Metallocene catalyst compositions and polymerization process therewith

ABSTRACT

This invention relates bisindenyl metallocene catalyst compounds having long (at least 4 carbon atoms) linear alkyl groups substituted at the two position and substituted or unsubstituted aryl groups at the four position and process using such catalyst compounds, particularly in the solution process at higher temperatures.

RELATED APPLICATIONS AND PATENTS

This application is the § 371 National Stage application forPCT/US2016/034784, filed May 27, 2016. This invention relates to:PCT/US2016/034755, filed May 27, 2016, which has entered the UnitedStates National Phase as U.S. Ser. No. 15/570,809, PCT/US2016/034768,filed May 27, 2016, which has entered the United States National Phaseas U.S. Ser. No. 15/570,814.

FIELD OF THE INVENTION

This invention relates to novel catalyst compounds, catalyst systemscomprising asymmetric substituted indenyl groups and uses thereof.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hence,there is interest in finding new catalyst systems that increase thecommercial usefulness of the catalyst and allow the production ofpolymers having improved properties.

Catalysts for olefin polymerization are often based on metallocenes ascatalyst precursors, which are typically activated either with analumoxane or with an activator containing a non-coordinating anion.Metallocene catalysts for propylene copolymers, however, have beenlimited by their inability to produce propylene-ethylene copolymers ofhigh molecular weight or other desired properties. This has beenobserved for many metallocene structures, such as the syndiospecificC_(s) symmetric Me₂C(Cp)(Flu)ZrCl₂, the aspecific C_(2v) symmetricMe₂Si(Flu)₂ZrCl₂, and both the C₂ symmetric rac-Me₂C(3-iPr-Ind)₂ZrCl₂and the fluxional (2-Ph-Ind)₂ZrCl₂ catalysts for elastomericpolypropylene. This deficit has also been found for the isospecific C₂symmetric rac-Me₂Si(2-Me-4,5-Benz-Ind)₂ZrCl₂ andrac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂ (L. Resconi, C. Fritze, “MetalloceneCatalysts for Propylene Polymerization” In Polypropylene Handbook (N.Pasquini, Ed.), ch. 2.2, Hanser Publishers, Munic 2005). It is thoughtthat, while the 2-Me substitution of this catalyst family suppresses theβ-hydrogen transfer to the propylene monomer and thus prevents theformation of low molecular weight polymer, it fails to prevent theβ-hydrogen transfer to the ethylene comonomer in case of the latter'spresence. This β-hydrogen transfer to the ethylene comonomer becomes thefavored chain termination mechanism and leads to the formation of lowmolecuar weight propylene-ethylene copolymers (A. Tynys et al.,Macromol. Chem. Phys. 2005, vol. 206, pp. 1043-1056: “Ethylene-PropyleneCopolymerizations: Effect of Metallocene Structure on TerminationReactions and Polymer Microstructure”). Exceptions have been found insome zirconocenes with bulky ligands, such as rac-Me₂C(3-tBu-Ind)₂ZrCl₂,which show a marked increase in molecular weight by ethyleneincorporation. This catalyst, however, has shortcomings in terms ofhomopolymer molecular weight and activity.

Desirable metallocene catalysts for isotactic polypropylene productionproduce polypropylenes with high melting points. This thought to be dueto high stereospecificity and/or regioselectivity in the polymermicrostructure. Within the rac-Alk₂Si(2-Alk-Ind)₂ZrCl₂ catalyst family(Alk=Alkyl), the stereospecificity and regioselectivity is continuouslybeing modified. For Example, EP 834 519 A1 relates torac-Me₂Si(2-Me-4-Ar-Ind)₂ZrCl₂ type metallocenes for the production ofrigid, high melting point polypropylenes with high stereoregularity andvery low amounts of regio errors. However, these polypropylenes did notfare well under commercially relevant process conditions and sufferedfrom low activity/productivity-levels.

US-A1 2001/0053833 discloses metallocenes where the 2-position issubstituted with an unsubstituted heteroaromatic ring or aheteroaromatic ring having at least one substituent bonded to the ringthat produce propylene ethylene copolymers having less than desiredmelting points.

WO 01/058970 relates to impact copolymers having a high melting pointand a good rubber content, produced by catalysts of therac-Me₂Si(2-Alk-4-Ar-Ind)₂ZrCl₂ family when both alkyl substituents wereiso-propyl groups. However, these catalysts suffer from activity issues.

WO 02/002576 discloses bridged metallocenes of the(2-Alkyl-4-Ph-Ind)₂ZrCl₂ family where the 2-positions can be isopropyland the Ph substituents are substituted in the 3 and 5 positions,particularly with t-butyl. However, these catalysts also suffer fromactivity/productivity issues at commercial conditions.

WO 03/002583 discloses bridged metallocenes of the(2-Alkyl-4-Ph-Ind)₂ZrCl₂ family where the 2-positions may be substitutedwith isopropyl groups and the 4 positions are substituted with Ph groupsubstituted at the 2-position, particularly with a phenyl group.

However, these catalysts also suffer from activity/productivity issuesat commercial conditions. In addition, these catalysts have relativelylow Mw capabilities for isotactic homopolypropylene.

EP-A2 1 250 365; WO 97/40075; and WO 03/045551 relate to bis indenylmetallocenes where substituents at the 2-positions of either of theindenyl ligands are branched or cyclicized in the α-position. However,these catalysts still have relatively limited Mw capabilities forisotactic homopolypropylene.

WO 04/106351 relates to bisindenyl metallocenes having substitutents inthe 2-positions of the indenyl ligands with the proviso that one ligandis unbranched or bound via an sp²-hybridized carbon atom and the otherligand is branched in the α-position. However, these catalysts stillhave relatively limited Mw capabilities for isotactic homopolypropylene.

U.S. Pat. No. 8,507,706 discloses bisindenyl metallocenes where at leastone 2 position on the indenyl groups is substituted with a groupbranched at the beta position and the other 2-position is not branchedat the alpha position. US 2011/0230630 discloses similar metallocenesexcept that the group at the 2 position is branched in the beta-positionand that the beta-carbon atom is a quarternary carbon atom and part of anon-cyclic hydrocarbon system.

U.S. Pat. No. 7,829,495 discloses alkyl substituted metallocenes havinga “ . . . C₃ or greater hydrocarbyl . . . substitutent bonded to eitherthe LA or LB ring through a primary carbon atom . . . preferably ann-alkyl substituent . . . ” (see column 4, lines 9-12). Further, in theExamples section,(n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdichloride combined with methylalumoxane and Davision™ 948 silica isused for ethylene hexene polymerization; bis(n-propyl cyclopentadienyl)zirconium dichloride combined with methylalumoxane and Davision™ 948silica is used for ethylene hexene polymerization; anddimethylsilyl(flourenyl)(n-propyl cyclopentadienyl) zirconium dichloridecombined with methylalumoxane and Davision silica is used for ethylenehexene polymerization.

US 2015/0025208, published Jan. 22, 2015, discloses bridged bisindenylcompounds where the 2 positions on the indene (R² and R⁸) are not thesame and the 4 positions on the indene (R⁴ and R¹⁰) are substitutedphenyl groups, where at least one of R⁴ and R¹⁰ is a phenyl groupsubstituted at the 3 and 5 position.

US 2005/0182266 discloses a process for preparing transition metalcompounds having a specific substitution pattern, the correspondingtransition metal compounds themselves and their use in the preparationof catalyst systems and also the use of the catalyst systems in thepolymerization and copolymerization of olefins.

Other references of interest include U.S. Pat. Nos. 6,051,727;6,255,506; EP 0 576 970; U.S. Pat. Nos. 5,459,117; 5,532,396; 5,543,373;5,585,509; 5,631,202; 5,696,045; 5,700,886; 6,492,465; 6,150,481;5,770,753; 5,786,432; 5,840,644; 6,242,544; 5,869,584; 6,399,533;6,444,833; 6,559,252; 6,608,224; 6,635,779; 6,841,501; 6,878,786;6,949,614; 6,953,829; 7,034,173; 7,141,527; 7,314,903; 7,342,078;7,405,261; 7,452,949; 7,569,651; 7,615,597; 7,799,880; 7,964,679;7,985,799; 8,222,356; 5,278,264; 5,276,208; 5,049,535; US 2011/0230630;WO 02/002575; WO 02/022575; WO 2003/002583; U.S. Pat. No. 7,122,498; US2011/0230630; US 2010/0267907; EP 1 250 365; WO 97/9740075; WO03/045551; WO 02/002576; US 2015/0025205; U.S. Ser. No. 14/572,195;filed Dec. 16, 2014; U.S. Pat. No. 9,193,856; WO 2004/052945; US2016/0032025; and Journal of Molecular Catalysis A: Chemical (20010705),172(1-2), pp. 43-65.

This invention relates to co-owned U.S. Pat. No. 9,249,239 andco-pending applications U.S. Ser. No. 15/000,731, filed Jan. 19, 2016;U.S. Ser. No. 14/324,333, filed Jul. 7, 2014; U.S. Ser. No. 14/324,408,filed Jul. 7, 2014; and U.S. Ser. No. 14/324,427, filed Jul. 7, 2014.

There is still a need in the art for new and improved catalyst systemsfor the polymerization of olefins, in order to achieve specific polymerproperties, such as high melting point, high molecular weights, toincrease conversion or comonomer incorporation, or to alter comonomerdistribution without deteriorating the resulting polymer's properties.

It is therefore an object of the present invention to provide novelcatalyst compounds, catalysts systems comprising such compounds, andprocesses for the polymerization of olefins using such compounds andsystems.

Furthermore, it is an objective of the present invention to provideolefin polymers, particularly propylene homopolymers, and randomcopolymers of propylene with ethylene and/or higher alpha-olefins.

SUMMARY OF THE INVENTION

This invention relates to metallocene catalyst compounds represented bythe formula:

wherein,

R² and R⁸ are, independently, a C1 to C20 linear alkyl group, providedthat at least one of R² and R⁸ must have at least 4 carbon atoms;

R⁴ and R¹⁰ are substituted or unsubstituted aryl groups, provided thatat least one of the aryl groups is: 1) substituted at an othro positionwith at least one group selected from C₁ to C₄₀ hydrocarbyls,heteroatoms, and heteroatom containing groups and/or 2) substituted atthe 3′, 4′ or 5′ position with at least one group selected from C₁ toC₄₀ hydrocarbyls, heteroatoms, and heteroatom containing groups;

M is a group 2, 3 or 4 transition metal;

T is a bridging group;

each X is an anionic leaving group;

each R¹, R³, R⁵, R⁶, R⁷, R⁹, R¹¹, R¹², R¹³, and R¹⁴ is, independently,hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, silylcarbyl, substituted silylcarbyl,germylcarbyl, or substituted germylcarbyl substituents.

This invention further relates to a catalyst system comprising suchmetallocenes and an activator.

This invention further relates to a method to polymerize olefinscomprising contacting olefins with a catalyst system comprising saidmetallocene catalyst compound(s) described above and an activator.

This invention further relates to a method to polymerize olefinscomprising contacting at a temperature of 60° C. (alternately 80° C.) ormore, olefins and with a catalyst system comprising an activator and oneor more catalyst compounds described above, and preferably obtainingpolymer having: a) from 0.5 to 60 weight % ethylene, based upon theweight of the copolymer; b) an Mw of 200,000 g/mol or more, asdetermined by GPC-DRI.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a drawing of the formulas for MCNs 1 to 14.

FIG. 2 is a graph of Mw versus ethylene feed pressure from Table 1 (dataaveraged over two runs except for condition “MNC7, 120 psi C2”).

FIG. 3 is a graph of Mw versus C2 wt % incorporation from Table 2.

FIG. 4 is a graph of Mw versus C2 wt % incorporation from Table 3.

FIG. 5 is a graph of iPP melting point versus polymerization temperaturedata from Table 4 (data averaged over two runs).

FIG. 6 is a graph of Mw versus polymerization temperature data fromTable 4 (data averaged over two runs).

FIG. 7 is a graph of activity versus ethylene feed pressure data fromTable 4 (data averaged over two runs).

FIG. 8 is a graph of Mw versus ethylene feed pressure data from Table 4(data averaged over two runs).

FIG. 9 is a GPC-3D graph for the polymer made in Examples 163 (left) and164 (right).

FIG. 10 is a graph of rheological measurements or the polymer made inExamples 163 (left) and 164 (right).

FIG. 11 is a graph of phase angle versus complex modulus for the polymermade in Examples 163 and 164.

FIG. 12 is a graph of complex shear viscosity versus frequency for thepolymer made in Examples 163 and 164.

FIG. 13 is a reaction scheme for synthesis of metallocenes.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as described inCHEMICAL AND ENGINEERING NEWS, 63(5), p. 27 (1985). Therefore, a “Group4 metal” is an element from Group 4 of the Periodic Table.

Unless otherwise indicated, “catalyst productivity” is a measure of howmany grams of polymer (P) are produced using a polymerization catalystcomprising W g of catalyst (cat), over a period of time of T hours; andmay be expressed by the following formula: P/(T x W) and expressed inunits of gPgcat⁻¹ hr⁻¹. Unless otherwise indicated, “catalyst activity”is a measure of how active the catalyst is and is reported as the massof product polymer (P) produced per mole of catalyst (cat) used(kgP/molcat). Unless otherwise indicated, “conversion” is the amount ofmonomer that is converted to polymer product, and is reported as mol %and is calculated based on the polymer yield and the amount of monomerfed into the reactor.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, the olefin present in such polymer or copolymer is thepolymerized form of the olefin. For example, when a copolymer is said tohave an “ethylene” content of 35 wt % to 55 wt %, it is understood thatthe mer unit in the copolymer is derived from ethylene in thepolymerization reaction and said derived units are present at 35 wt % to55 wt %, based upon the weight of the copolymer. A “polymer” has two ormore of the same or different mer units. A “homopolymer” is a polymerhaving mer units that are the same. A “copolymer” is a polymer havingtwo or more mer units that are different from each other. A “terpolymer”is a polymer having three mer units that are different from each other.“Different” as used to refer to mer units indicates that the mer unitsdiffer from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An “ethylene polymer” or “ethylenecopolymer” is a polymer or copolymer comprising at least 50 mole %ethylene derived units, a “propylene polymer” or “propylene copolymer”is a polymer or copolymer comprising at least 50 mole % propylenederived units, and so on.

For the purposes of this invention, ethylene shall be considered anα-olefin.

For purposes of this invention and claims thereto, the term“substituted” means that a hydrogen group has been replaced with aheteroatom, or a heteroatom containing group. For example, a“substituted hydrocarbyl” is a radical made of carbon and hydrogen whereat least one hydrogen is replaced by a heteroatom or heteroatomcontaining group.

Unless otherwise indicated, room temperature is 23° C.

“Different” or “not the same” as used to refer to R groups in anyformula herein (e.g., R² and R⁸ or R⁴ and R¹⁰) or any substituent hereinindicates that the groups or substituents differ from each other by atleast one atom or are different isomerically.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, and Mz is z average molecular weight, wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD), also referred to as polydispersity index (PDI), is defined to beMw divided by Mn. Unless otherwise noted, all molecular weight units(e.g., Mw, Mn, Mz) are reported in units of g/mol. The followingabbreviations may be used herein: Me is methyl, Et is ethyl, Pr ispropyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu isbutyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu istert-butyl, Oct is octyl, Ph is phenyl, Bn is benzyl, MAO ismethylalumoxane.

A “catalyst system” is combination of at least one catalyst compound, atleast one activator, an optional co-activator, and an optional supportmaterial. For the purposes of this invention and the claims thereto,when catalyst systems are described as comprising neutral stable formsof the components, it is well understood by one of ordinary skill in theart, that the ionic form of the component is the form that reacts withthe monomers to produce polymers.

In the description herein, the metallocene catalyst may be described asa catalyst precursor, a pre-catalyst compound, metallocene catalystcompound or a transition metal compound, and these terms are usedinterchangeably. An “anionic ligand” is a negatively charged ligandwhich donates one or more pairs of electrons to a metal ion.

A metallocene catalyst is defined as an organometallic compound with atleast one π-bound cyclopentadienyl moiety (or substitutedcyclopentadienyl moiety) and more frequently two π-boundcyclopentadienyl moieties or substituted cyclopentadienyl moietiesbonded to a transition metal.

For purposes of this invention and claims thereto in relation tometallocene catalyst compounds, the term “substituted” means that ahydrogen group has been replaced with a hydrocarbyl group, a heteroatom,or a heteroatom containing group. For example, methyl cyclopentadiene(Cp) is a Cp group substituted with a methyl group.

For purposes of this invention and claims thereto, “alkoxides” includethose where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl groupmay be straight chain, branched, or cyclic. The alkyl group may besaturated or unsaturated. In some embodiments, the alkyl group maycomprise at least one aromatic group.

“Asymmetric” as used in connection with the instant indenyl compoundsmeans that the substitutions at the 4 positions are different, or thesubstitutions at the 2 positions are different, or the substitutions atthe 4 positions are different and the substitutions at the 2 positionsare different.

Metallocene Catalyst Compounds

The invention relates to a metallocene catalyst compound represented bythe formula:

wherein,

R² and R⁸ are may be the same or different and each is, independently aC₁ to C₂₀ linear alkyl group, provided at at least one of R² and R⁸ hasat least 4 carbon atoms, preferably at least 6 carbon atoms, preferablyR² and R⁸ have no branches at the alpha or beta positions;

R⁴ and R¹⁰ are substituted or unsubstituted aryl groups (such assubstituted or unsubstituted phenyl groups, preferably substitutedphenyl groups), provided that at least one of the aryl groups is: 1)substituted at an othro position with at least one group selected fromC₁ to C₄₀ hydrocarbyls, heteroatoms, and heteroatom containing groupsand/or 2) substituted at the 3′, 4′ or 5′ position with at least onegroup selected from C₁ to C₄₀ hydrocarbyls, heteroatoms, and heteroatomcontaining groups;

M is a group 2, 3 or 4 transition metal, preferably group 4 transitionmetal;

T is a bridging group;

each X is an anionic leaving group;

each R¹, R³, R⁵, R⁶, R⁷, R⁹, R¹¹, R¹², R¹³, and R¹⁴ is, independently,hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, silylcarbyl, substituted silylcarbyl,germylcarbyl, or substituted germylcarbyl substituents.

In any embodiment described herein, R² may be a linear C₁-C₁₀ alkylgroup, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,n-heptyl, n-octyl, n-nonyl or n-decyl) which may be halogenated,preferably with I, F, Cl or Br.

In any embodiment described herein, R⁸ is a linear C₁-C₁₀ alkyl group,preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,n-heptyl, n-octyl, n-nonyl or n-decyl) which may be halogenated,preferably with I, F, Cl or Br.

In some embodiments of the invention, R² and R⁸ are the same linearalkyl group, such as n-butyl, n-hexyl, etc.

In alternate embodiments, R² and R⁸ are different, such as R² is methyland R⁸ is n-butyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl.

By “substituted phenyl group” is meant a phenyl is substituted with 1,2, 3, 4, or 5 C₁ to C₂₀ substituted or unsubstituted hydrocarbyl groups,such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, phenyl, substituted phenyl, biphenyl oran isomer thereof. In useful embodiments, the phenyl group issubstituted at the meta or para positions, preferably the 3′ and/or 5′positions, preferably with C4 to C12 alkyl groups. Alternately thephenyl group may be substituted at the 2′ position, but is preferablynot substituted in the 2′ and 6′ positions, e.g., in a preferredembodiment of the invention when the 2′ position of the phenyl issubstituted, the 6′ position is H). Alternately, the phenyl group may besubstituted at the 4′ position, with a group of the formula (XR′_(n))⁻,wherein X is a Group 14, 15, 16, or 17 heteroatom and R′ is one of ahydrogen atom, halogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ arylgroup and n is 0, 1, 2, or 3; preferably —NR′₂, —SR′, —OR′, —OSiR′₃,—SiR′₃, or —PR′₂; and optionally, one or more of the remaining positionson the phenyl are substituted, such as the 2′, 3′ and or 5′ positions.

In another aspect the 4′ position on the aryl group is not a C4 group,alternately is not a hydrocarbyl group.

In another aspect, R⁴ and R¹⁰ are independently substituted phenylgroups, preferably phenyl groups substituted with C₁ to a C₁₀ alkylgroups (such as t-butyl, sec-butyl, n-butyl, isopropyl, n-propyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, phenyl, mesityl, or adamantyl), or an aryl group which maybe further substituted with an aryl group, and the two aryl groups boundtogether can be joined together directly or by linker groups, whereinthe linker group is an alkyl, vinyl, phenyl, alkynyl, silyl, germyl,amine, ammonium, phosphine, phosphonium, ether, thioether, borane,borate, alane or aluminate groups.

In another aspect, at least one of R⁴ and R¹⁰ is (or optionally, bothare) a phenyl group substituted at the 3′ and 5′ position.

In another aspect, at least one of R⁴ and R¹⁰ is (or optionally, bothare) a phenyl group substituted at the 2′ position with an alkyl or anaryl group, such as a phenyl group.

In another aspect, at least one of R⁴ and R¹⁰ is (or optionally, bothare) a phenyl group substituted at the 3′ and 5′ position and at leastone of R⁴ and R¹⁰ is a phenyl group substituted at the 2′ position withan alkyl group or an aryl group, such as a phenyl group.

In yet another aspect, at least one of R⁴ and R¹⁰ is (or optionally,both are) a phenyl group substituted at the 3′ and 5′ positions with C₁to a C₁₀ alkyl groups, such as a tertiary butyl group.

In yet another aspect, at least one of R⁴ and R¹⁰ is a phenyl groupsubstituted at the 3′ and 5′ positions with C₁ to a C₁₀ alkyl groups,such as a tertiary butyl group and at least one of R⁴ and R¹⁰ is aphenyl group substituted at the 2′ position with an alkyl or an arylgroup, such as a phenyl group.

In yet another aspect, at least one of R⁴ and R¹⁰ is a phenyl groupsubstituted at the 3′ and 5′ positions with C₁ to a C₁₀ alkyl groups,such as a tertiary butyl group and at the 4′ position with (XR′_(n))⁻,wherein X is a Group 14, 15, 16 or 17 heteroatom having an atomic weightof 13 to 79, R′ is one of a hydrogen atom, halogen atom, a C₁-C₁₀ alkylgroup, or a C₆-C₁₀ aryl group, and n is 0, 1, 2, or 3, such as methoxy,and at least one of R⁴ and R¹⁰ is a phenyl group substituted at the 2′position with an alkyl or an aryl group, such as a phenyl group.

In yet another aspect, both R⁴ and R¹⁰ are a phenyl group substituted atthe 3′ and 5′ positions with C₁ to a C₁₀ alkyl groups, such as atertiary butyl group.

In still another aspect, at least one of R⁴ and R¹⁰ is a phenyl groupsubstituted at the 3′ and 5′ positions with aryl groups, such assubstituted or unsubstituted phenyl groups.

In still another aspect, both R⁴ and R¹⁰ are a phenyl group substitutedat the 3′ and 5′ positions with aryl groups, such as substituted orunsubstituted phenyl groups.

In another aspect, at least one of R⁴ and R¹⁰ is an aryl groupsubstituted at 3′ and 5′ positions with C₁ to a C₁₀ alkyl groups (suchas t-butyl, sec-butyl, n-butyl, isopropyl, n-propyl, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl,mesityl, or adamantyl) or aryl groups and combinations thereof, wherein,when R⁴ or R¹⁰ is a phenyl group which is further substituted with anaryl group, the two groups bound together can be joined togetherdirectly or by linker groups, wherein the linker group is an alkyl,vinyl, phenyl, alkynyl, silyl, germyl, amine, ammonium, phosphine,phosphonium, ether, thioether, borane, borate, alane or aluminategroups.

Alternately, when at least one of R⁴ and R¹⁰ is a phenyl groupsubstituted at 3′ and 5′ positions, the phenyl group may also besubstituted at the 4′ position, preferably with a substituent isselected from (XR′_(n))⁻, wherein X is a Group 14, 15, 16 or 17heteroatom having an atomic weight of 13 to 79 (preferably N, O, S, P,or Si) and R′ is one of a hydrogen atom, halogen atom, a C₁-C₁₀ alkylgroup (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl,nonyl, decyl or an isomer thereof), or a C₆-C₁₀ aryl group and n is 0,1, 2, or 3; preferably (XR′_(n))⁻ is —NR′₂, —SR′, —OR′, —OSiR′₃, —SiR′₃,or —PR′₂, preferably (XR′)⁻ is —NR′₂, —SR′, —OR′, —OSiR′₃, or —PR′₂,preferably (XR′)⁻ is —SR′, —OR′, or —OSiR′₃, preferably (XR′)⁻ is —NR′₂or —PR′₂, or preferably (XR′)⁻ is —OR′ m preferably where R′ is a C₁-C₁₀alkyl group, particularly a methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, iso-butoxy, sec-butoxy, or t-butoxy group, most particularlymethoxy.

In yet another aspect, M is Hf, Ti and/or Zr, particularly Hf and/or Zr,particularly Zr.

Suitable radicals for the each of the groups R¹, R³, R⁵, R⁶, R⁷, R⁹,R¹¹, R¹², R¹³, and R¹⁴ are independently selected from hydrogen orhydrocarbyl radicals including methyl, ethyl, ethenyl, and all isomers(including cyclics such as cyclohexyl) of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, propenyl, butenyl, andfrom halocarbyls and all isomers of halocarbyls includingperfluoropropyl, perfluorobutyl, perfluoroethyl, perfluoromethyl, andfrom substituted hydrocarbyl radicals and all isomers of substitutedhydrocarbyl radicals including trimethylsilylpropyl,trimethylsilylmethyl, trimethylsilylethyl, and from phenyl, and allisomers of hydrocarbyl substituted phenyl including methylphenyl,dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl,diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl,tripropylphenyl, dimethylethylphenyl, dimethylpropylphenyl,dimethylbutylphenyl, dipropylmethylphenyl, and the like; from allisomers of halo substituted phenyl (where halo is, independently,fluoro, chloro, bromo and iodo) including halophenyl, dihalophenyl,trihalophenyl, tetrahalophenyl, and pentahalophenyl; and from allisomers of halo substituted hydrocarbyl substituted phenyl (where halois, independently, fluoro, chloro, bromo and iodo) includinghalomethylphenyl, dihalomethylphenyl, (trifluoromethyl)phenyl,bis(triflouromethyl)phenyl; and from all isomers of benzyl, and allisomers of hydrocarbyl substituted benzyl including methylbenzyl,dimethylbenzyl.

In other embodiments of the invention, each X is, independently,selected from the group consisting of hydrocarbyl radicals having from 1to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,halides, dienes, amines, phosphines, ethers, and a combination thereof,(two X's may form a part of a fused ring or a ring system).

Suitable examples for X include chloride, bromide, fluoride, iodide,hydride, and C₁ to C₂₀ hydrocarbyls, preferably methyl, ethyl, propyl,butyl, pentyl, hexyl, phenyl, benzyl, and all isomers thereof, or two Xtogether are selected from C₄ to C₁₀ dienes, preferably butadiene,methylbutadiene, pentadiene, methylpentadiene, dimethylpentadiene,hexadiene, methylhexadiene, dimethylhexadiene, or from C₁ to C₁₀alkylidenes, preferably methylidene, ethylidene, propylidene, or from C₃to C₁₀ alkyldiyls, preferably propandiyl, butandiyl, pentandiyl, andhexandiyl. In particular, X is chloride or methyl.

In any embodiment, T is a bridging group selected from R′₂C, R′₂Si,R′₂Ge, R′₂CCR′₂, R′₂CCR′₂CR′₂, R′C═CR′, R′C═CR′CR′₂, R′₂CSiR′₂,R′₂SiSiR′₂, R′₂CSiR′₂CR′₂, R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂, R′₂CGeR′₂,R′₂GeGeR′₂, R′₂CGeR′₂CR′₂, R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂, R′C═CR′GeR′₂,R′B, R′₂C—BR′, R′₂C—BR′—CR′₂, R′N, R′₂C—NR′, R′₂C—NR′—CR′₂, R′P,R′₂C—PR′, and R′₂C—PR′—CR′₂ where R′ is, independently, hydrogen,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, or germylcarbyl, and two or more R′ on the sameatom or on adjacent atoms may join together to form a substituted orunsubstituted, saturated, partially unsaturated, or aromatic cyclic orpolycyclic substituent.

Suitable examples for the bridging group T includedihydrocarbylsilylenes including dimethylsilylene, diethylsilylene,dipropylsilylene, dibutylsilylene, dipentylsilylene, dihexylsilylene,methylphenylsilylene, diphenylsilylene, dicyclohexylsilylene,methylcyclohexylsilylene, dibenzylsilylene, tetramethyldisilylene,cyclotrimethylenesilylene, cyclotetramethylenesilylene,cyclopentamethylenesilylene, divinylsilylene, andtetramethyldisiloxylene; dihydrocarbylgermylenes includingdimethylgermylene, diethylgermylene, dipropylgermylene,dibutylgermylene, methylphenylgermylene, diphenylgermylene,dicyclohexylgermylene, methylcyclohexylgermylene,cyclotrimethylenegermylene, cyclotetramethylenegermylene, andcyclopentamethylenegermylene; carbylenes and carbdiyls includingmethylene, dimethylmethylene, diethylmethylene, dibutylmethylene,dipropylmethylene, diphenylmethylene, ditolylmethylene,di(butylphenyl)methylene, di(trimethylsilylphenyl)methylene,dibenzylmethylene, cyclotetramethylenemethylene,cyclopentamethylenemethylene, ethylene, methylethylene,dimethylethylene, trimethylethylene, tetramethylethylene,cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene,propanediyl, methylpropanediyl, dimethylpropanediyl,trimethylpropanediyl, tetramethylpropanediyl, pentamethylpropanediyl,hexamethylpropanediyl, vinylene, and ethene-1,1-diyl; boranediylsincluding methylboranediyl, ethylboranediyl, propylboranediyl,butylboranediyl, pentylboranediyl, hexylboranediyl,cyclohexylboranediyl, and phenylboranediyl; and combinations thereofincluding dimethylsilylmethylene, diphenylsilylmethylene,dimethylsilylethylene, methylphenylsilylmethylene.

In particular, T is CH₂, CH₂CH₂, C(CH₃)₂, SiMe₂, SiPh₂, SiMePh,Si(CH₂)₃, Si(CH₂)₄, Si(Me₃SiPh)₂, or Si(CH₂)₅.

In another embodiment, T is represented by the formula R₂ ^(a)J, where Jis C, Si, or Ge, and each R^(a) is, independently, hydrogen, halogen, C₁to C₂₀ hydrocarbyl or a C₁ to C₂₀ substituted hydrocarbyl, and two R^(a)can form a cyclic structure including aromatic, partially saturated, orsaturated cyclic or fused ring system.

In a preferred embodiment of the invention in any formula describedherein, T is represented by the formula, (R*₂G)_(g), where each G is C,Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen,halogen, C1 to C20 hydrocarbyl or a C1 to C20 substituted hydrocarbyl,and two or more R* can form a cyclic structure including aromatic,partially saturated, or saturated cyclic or fused ring system.

In aspects of the invention, the rac/meso ratio of the metallocenecatalyst is 50:1 or greater, or 40:1 or greater, or 30:1 or greater, or20:1 or greater, or 15:1 or greater, or 10:1 or greater, or 7:1 orgreater, or 5:1 or greater.

In an embodiment of the invention, the metallocene catalyst comprisesgreater than 55 mol % of the racemic isomer, or greater than 60 mol % ofthe racemic isomer, or greater than 65 mol % of the racemic isomer, orgreater than 70 mol % of the racemic isomer, or greater than 75 mol % ofthe racemic isomer, or greater than 80 mol % of the racemic isomer, orgreater than 85 mol % of the racemic isomer, or greater than 90 mol % ofthe racemic isomer, or greater than 92 mol % of the racemic isomer, orgreater than 95 mol % of the racemic isomer, or greater than 98 mol % ofthe racemic isomer, based on the total amount of the racemic and mesoisomer-if any, formed. In a particular embodiment of the invention, themetallocene, especially the bridged bis(indenyl)metallocene, compoundconsists essentially of the racemic isomer.

Amounts of rac and meso isomers are determined by proton NMR. ¹H NMRdata are collected at 23° C. in a 5 mm probe using a 400 MHz Brukerspectrometer with deuterated methylene chloride or deuterated benzene.Data is recorded using a maximum pulse width of 45°, 8 seconds betweenpulses and signal averaging 16 transients. The spectrum is normalized toprotonated methylene chloride in the deuterated methylene chloride,which is expected to show a peak at 5.32 ppm.

In a preferred embodiment in any of the processes described herein onecatalyst compound is used, e.g., the catalyst compounds are notdifferent. For purposes of this invention one metallocene catalystcompound is considered different from another if they differ by at leastone atom. For example, “bisindenyl zirconium dichloride” is differentfrom (indenyl)(2-methylindenyl) zirconium dichloride” which is differentfrom “(indenyl)(2-methylindenyl) hafnium dichloride.” Catalyst compoundsthat differ only by isomer are considered the same for purposes if thisinvention, e.g., rac-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethylis considered to be the same as meso-dimethylsilylbis(2-methyl4-phenyl)hafnium dimethyl.

In some embodiments, two or more different catalyst compounds arepresent in the catalyst system used herein. In some embodiments, two ormore different catalyst compounds are present in the reaction zone wherethe process(es) described herein occur. When two transition metalcompound based catalysts are used in one reactor as a mixed catalystsystem, the two transition metal compounds should be chosen such thatthe two are compatible. A simple screening method such as by ¹H or ¹³CNMR, known to those of ordinary skill in the art, can be used todetermine which transition metal compounds are compatible. It ispreferable to use the same activator for the transition metal compounds,however, two different activators, such as a non-coordinating anionactivator and an alumoxane, can be used in combination. If one or moretransition metal compounds contain an X₁ or X₂ ligand which is not ahydride, hydrocarbyl, or substituted hydrocarbyl, then the alumoxane istypically contacted with the transition metal compounds prior toaddition of the non-coordinating anion activator.

The transition metal compounds (pre-catalysts) may be used in any ratio.Preferred molar ratios of (A) transition metal compound to (B)transition metal compound fall within the range of (A:B) 1:1000 to1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1,alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, andalternatively 5:1 to 50:1. The particular ratio chosen will depend onthe exact pre-catalysts chosen, the method of activation, and the endproduct desired. In a particular embodiment, when using the twopre-catalysts, where both are activated with the same activator, usefulmole percents, based upon the molecular weight of the pre-catalysts, are10 to 99.9% A to 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50%B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99%A to 1 to 10% B.

Methods to Prepare the Catalyst Compounds

Generally, metallocenes of this type are synthesized as shown in FIG. 13where (i) is a deprotonation via a metal salt of alkyl anion (e.g.,^(n)BuLi) to form an indenide. (ii) reaction of indenide with anappropriate bridging precursor (e.g., Me₂SiCl₂). (iii) reaction of theabove product with AgOTf. (iv) reaction of the above triflate compoundwith another equivalent of indenide. (v) double deprotonation via analkyl anion (e.g. ^(n)BuLi) to form a dianion (vi) reaction of thedianion with a metal halide (e.g., ZrCl₄). The final products areobtained by recrystallization of the crude solids where Ar₁ and Ar₂ areas defined for R⁴ and R¹⁰, and R₁ and R₂ are defined for R² and R⁸.

Catalyst compounds useful herein include:Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Me-4-(3′1,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Ph₂Si(4-oPh₂-2-nC₈-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Me-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Et-4-(3,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Et-4-(3′,5-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Et-4-(3′,5-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Et-4-(3,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Et-4-(3,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Et-4-(3,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-nPr-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-nPr-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Et-4-(3,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Et-4-(3,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-Et-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-Et-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-n-propyl-4-(3′,5-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-nC₃₋₄-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(2-nC₃₋₄-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(2-nPr-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(2-nPr-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(2-n-propyl-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(2-n-propyl-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(2-nC₃₋₄-(3′1,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(2-n-propyl-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)₂ZrCl₂; Me₂Si(4-oPh₂-2-nC₅-Ind)₂ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)₂ZrCl₂; Me₂Si(4-oPh₂-2-nC₇-Ind)₂ZrCl₂;Me₂Si₂(4-oPh₂-2-nC₈-Ind)₂ZrCl₂; Me₂Si(4-oPh₂-2-nC₉-Ind)₂ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)₂ZrCl₂;Me₂Si(2-nBu-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₅-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)₂ZrCl₂;Me₂Si₂(2-n-hexyl-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₇-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₈-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₉-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₁₀-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)₂ZrCl₂;Me₂Si(2-nBu-4-(3′,5′-tBu₂Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₅-4-(3′,5′-tBu₂Ph)-Ind)₂ZrCl₂;Me₂Si(2-n-hexyl-4-(3′,5′-tBu₂Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₇-4-(3′,5′-tBu₂Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₈-4-(3′,5′-tBu₂Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₉-4-(3′,5′-tBu₂Ph)-Ind)₂ZrCl₂;Me₂Si(2-nC₁₀-4-(3′,5′-tBu₂Ph)-Ind)₂ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)(2-nBu-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)(2-nC₅-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)(2-n-hexyl-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)(2-nC₇-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)(2-nC₈-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)(2-nC₉-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)(2-nC₁₀-4-(3′,5′-tBu₂-4′-OMe-Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂Ph)-Ind)(2-nBu-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂Ph)-Ind)(2-nC₅-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂Ph)-Ind)(2-n-hexyl-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂Ph)-Ind)(2-nC₇-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂Ph)-Ind)(2-nC₈-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂Ph)-Ind)(2-nC₉-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(2-Me-4-(3′,5′-tBu₂Ph)-Ind)(2-nC₁₀-4-(3′,5′-tBu₂Ph)-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-oPh₂-2-nBu-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-oPh₂-2-nC₅-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-oPh₂-2-nC₆-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-oPh-2-nC₇-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-oPh₂-2-nC₈-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-oPh₂-2-nC₉-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-oPh₂-2-nC₁₀-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Et-Ind)(4-oPh₂-2-nBu-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Et-Ind)(4-oPh₂-2-nC₅-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Et-Ind)(4-oPh₂-2-nC₆-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Et-Ind)(4-oPh₂-2-nC₇-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Et-Ind)(4-oPh₂-2-nC₈-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Et-Ind)(4-oPh-2-nC₉-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-Et-Ind)(4-oPh₂-2-nC₁₀-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-n-propyl-Ind)(4-oPh₂-2-nBu-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-n-propyl-Ind)(4-oPh₂-2-nC₅-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-n-propyl-Ind) (4-oPh₂-2-nC₆-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-n-propyl-Ind) (4-oPh₂-2-nC₇-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-n-propyl-Ind)(4-oPh-2-nC₈-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nPr-Ind))(4-oPh₂-2-nC₉-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nPr-Ind)(4-oPh-2-nC₁₀-Ind)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)₂ZrCl₂; Me₂Si(4-oPh₂-2-nC₅-Ind)₂ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)₂ZrCl₂; Me₂Si(4-oPh₂-2-nC₁₀-Ind)₂ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)₂ZrCl₂; Me₂Si(4-oPh₂-2-nC₉-Ind)₂ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)₂ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(4-(3′,5′-tBu₂-4′—OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrC₂;Me₂Si(4-oPh₂-2-nC_(s)-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₁₀-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(4-(3′,5′-tBu₂)-2-Me-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Et-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Et-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Et-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Et-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Et-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-Et-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-n-propyl-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-n-propyl-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₆-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-n-propyl-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₇-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-n-propyl-THI) ZrCl₂;Me₂Si(4-oPh₂-2-nC₈-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-n-propyl-THI) ZrCl₂;Me₂Si(4-oPh₂-2-nC₉-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-n-propyl-THI) ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nBu-THI) ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nC₅-THI) ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-n-hexyl-THI) ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nC₇-THI) ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nC₈-THI) ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nC₉-THI) ZrCl₂;Me₂Si(4-oPh₂-2-Me-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nC₁₀-THI) ZrCl₂;Me₂Si(4-oPh₂-2-nBu-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nBu-THI)ZrCl₂;Me₂Si(4-oPh₂-2-nC₅-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nC₅-THI) ZrCl₂;Me₂Si(4-oPh₂-2-n-hexyl-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-n-hexyl-THI)ZrCl₂; Me₂Si(4-oPh₂-2-nBu-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nC₇-THI)ZrCl₂;and Me₂Si(4-oPh₂-2-n-hexyl-Ind)(4-(3′,5′-tBu₂-4′-OMePh)-2-nC₈-THI)ZrCl₂,where oPh is orthophenyl, nC₆ is n-hexyl, t-Bu₂ and tBu₂ are di-tertiarybutyl, nBu is n-butyl, OMe is methoxy, Ind is indenyl, Ph is phenyl, nC₃and nPr are n-propyl, oPh₂ is ortho-biphenyl, nC₅ is n-pentyl, nC₇ isn-heptyl, nC₈ is n-octyl, nC₉ is n-nonyl, nC₁₀ is n-decyl, Me is methyl,Et is ethyl, THI is 1,5,6,7-tetrahydro-s-indacenyl, and OMe-Ph and OMePhare methoxyphenyl.

Activators

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxideor amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underpatent number U.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst compound (per metal catalytic site). Theminimum activator-to-catalyst-compound is a 1:1 molar ratio. Alternatepreferred ranges include from 1:1 to 1000:1, alternately from 1:1 to500:1 alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, oralternately from 1:1 to 50:1.

In an alternate embodiment, little or no alumoxane is used in thepolymerization processes described herein. Preferably, alumoxane ispresent at zero mole %, alternately the alumoxane is present at a molarratio of aluminum to catalyst compound transition metal less than 500:1,preferably less than 300:1, preferably less than 100:1, preferably lessthan 1:1.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to a cation or which is only weakly coordinated to acation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with this invention are those that arecompatible, stabilize the transition metal cation in the sense ofbalancing its ionic charge at +1, and yet retain sufficient lability topermit displacement during polymerization.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenylboron metalloid precursor or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459), or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium, and indium, or mixtures thereof.The three substituent groups are each independently selected fromalkyls, alkenyls, halogens, substituted alkyls, aryls, arylhalides,alkoxy, and halides. Preferably, the three groups are independentlyselected from halogen, mono or multicyclic (including halosubstituted)aryls, alkyls, and alkenyl compounds, and mixtures thereof, preferredare alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and arylgroups having 3 to 20 carbon atoms (including substituted aryls). Morepreferably, the three groups are alkyls having 1 to 4 carbon groups,phenyl, naphthyl, or mixtures thereof. Even more preferably, the threegroups are halogenated, preferably fluorinated, aryl groups. A preferredneutral stoichiometric activator is tris perfluorophenyl boron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP 0 570982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A;EP 0 277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741;5,206,197; 5,241,025; 5,384,299; 5,502,124; and U.S. Ser. No.08/285,380, filed Aug. 3, 1994; all of which are herein fullyincorporated by reference.

Preferred compounds useful as an activator in the process of thisinvention comprise a cation, which is preferably a Bronsted acid capableof donating a proton, and a compatible non-coordinating anion whichanion is relatively large (bulky), capable of stabilizing the activecatalyst species (the Group 4 cation) which is formed when the twocompounds are combined and said anion will be sufficiently labile to bedisplaced by olefinic, diolefinic and acetylenically unsaturatedsubstrates or other neutral Lewis bases, such as ethers, amines, and thelike. Two classes of useful compatible non-coordinating anions have beendisclosed in EP 0 277,003 A1, and EP 0 277,004 A1: 1) anioniccoordination complexes comprising a plurality of lipophilic radicalscovalently coordinated to and shielding a central charge-bearing metalor metalloid core; and 2) anions comprising a plurality of boron atomssuch as carboranes, metallacarboranes, and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and are preferably represented by thefollowing formula (II):(Z)_(d) ⁺(A^(d−))  (II)wherein Z is (L-H) or a reducible Lewis Acid, L is an neutral Lewisbase; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is anon-coordinating anion having the charge d−; and d is an integer from 1to 3.

When Z is (L-H) such that the cation component is (L-H)_(d) ⁺, thecation component may include Bronsted acids such as protonated Lewisbases capable of protonating a moiety, such as an alkyl or aryl, fromthe bulky ligand metallocene containing transition metal catalystprecursor, resulting in a cationic transition metal species. Preferably,the activating cation (L-H)_(d) ⁺ is a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such asdimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

When Z is a reducible Lewis acid it is preferably represented by theformula: (Ar₃C⁺), where Ar is aryl or aryl substituted with aheteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀hydrocarbyl, preferably the reducible Lewis acid is represented by theformula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀hydrocarbyl. In a preferred embodiment, the reducible Lewis acid istriphenyl carbenium.

The anion component A^(d−) include those having the formula[M^(k)+Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6,preferably 3, 4, 5 or 6; n−k=d; M is an element selected from Group 13of the Periodic Table of the Elements, preferably boron or aluminum, andQ is independently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide, and two Q groups may form a ring structure.Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20carbon atoms, more preferably each Q is a fluorinated aryl group, andmost preferably each Q is a pentafluoryl aryl group. Examples ofsuitable A^(d−) components also include diboron compounds as disclosedin U.S. Pat. No. 5,447,895, which is fully incorporated herein byreference.

In a preferred embodiment, this invention relates to a method topolymerize olefins comprising contacting olefins (preferably ethylene)with a catalyst compound and a boron containing NCA activatorrepresented by the formula (14):Z_(d) ⁺(A^(d−))  (14)where: Z is (L-H) or a reducible Lewis acid; L is an neutral Lewis base(as further described above); H is hydrogen; (L-H) is a Bronsted acid(as further described above); A^(d−) is a boron containingnon-coordinating anion having the charge d (as further described above);d is 1, 2, or 3.

In a preferred embodiment in any NCA represented by Formula 14 describedabove, the reducible Lewis acid is represented by the formula: (Ar₃C⁺),where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl, preferably thereducible Lewis acid is represented by the formula: (Ph₃C⁺), where Ph isphenyl or phenyl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl,or a substituted C₁ to C₄₀ hydrocarbyl.

In a preferred embodiment in any of the NCAs represented by Formula 14described above, Z_(d) ⁺ is represented by the formula: (L-H)_(d) ⁺,wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronstedacid; and d is 1, 2, or 3, preferably (L-H)_(d) ⁺ is a Bronsted acidselected from ammoniums, oxoniums, phosphoniums, silyliums, and mixturesthereof.

In a preferred embodiment in any of the NCAs represented by Formula 14described above, the anion component A^(d−) is represented by theformula [M*k*+Q*n*]d*⁻ wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or6 (preferably 1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* isindependently selected from hydride, bridged or unbridged dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbylradicals, said Q* having up to 20 carbon atoms with the proviso that innot more than 1 occurrence is Q* a halide.

This invention also relates to a method to polymerize olefins comprisingcontacting olefins (such as ethylene) with a catalyst compound and anNCA activator represented by the formula (I):R_(n)M**(ArNHal)_(4-n)  (I)where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula Ialso comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, preferably the cation is Z_(d) ⁺ as described above.

In a preferred embodiment in any of the NCAs comprising an anionrepresented by Formula I described above, R is selected from the groupconsisting of substituted or unsubstituted C₁ to C₃₀ hydrocarbylaliphatic or aromatic groups, where substituted means that at least onehydrogen on a carbon atom is replaced with a hydrocarbyl, halide,halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid,dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C₄ to C₂₀ hydrocarbyl groups; —SRI, —NR²², and —PR³²,where each R¹, R², or R³ is independently a substituted or unsubstitutedhydrocarbyl as defined above; or a C₁ to C₃₀ hydrocarbyl substitutedorganometalloid.

In a preferred embodiment in any of the NCAs comprising an anionrepresented by Formula I described above, the NCA also comprises cationcomprising a reducible Lewis acid represented by the formula: (Ar₃C⁺),where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl, preferably thereducible Lewis acid represented by the formula: (Ph₃C⁺), where Ph isphenyl or phenyl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl,or a substituted C₁ to C₄₀ hydrocarbyl.

In a preferred embodiment in any of the NCAs comprising an anionrepresented by Formula I described above, the NCA also comprises acation represented by the formula, (L-H)_(d) ⁺, wherein L is an neutralLewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or3, preferably (L-H)_(d) ⁺ is a Bronsted acid selected from ammoniums,oxoniums, phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. Nos. 7,297,653 and 7,799,879.

Another activator useful herein comprises a salt of a cationic oxidizingagent and a noncoordinating, compatible anion represented by the formula(16):(OX^(e+))_(d)(A^(d−))_(e)  (16)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above).

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) include tetrakis(pentafluorophenyl)borate.

In another embodiment, the catalyst compounds described herein can beused with Bulky activators. A “Bulky activator” as used herein refers toanionic activators represented by the formula:

where:each R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group); each R₃ is a halide,C₆ to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group ofthe formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl orhydrocarbylsilyl group (preferably R₃ is a fluoride or a C₆perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ can formone or more saturated or unsaturated, substituted or unsubstituted rings(preferably R₂ and R₃ form a perfluorinated phenyl ring);L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol; andwherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964.

Molecular volume (MV), in units of cubic Å, is calculated using theformula: MV=8.3V₅, where V_(s) is the scaled volume. V_(s) is the sum ofthe relative volumes of the constituent atoms, and is calculated fromthe molecular formula of the substituent using the following table ofrelative volumes. For fused rings, the V_(s) is decreased by 7.5% perfused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tableat column 20, line 35 et seq. of U.S. Pat. No. 9,266,977.

For a list of particularly useful Bulky activators please see U.S. Pat.No. 8,658,556, which is incorporated by reference herein.

In another embodiment, one or more of the NCA activators is chosen fromthe activators described in U.S. Pat. No. 6,211,105.

Preferred activators include N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph₃C+][B(C₆F₅)₄ ⁻], [Me₃NH⁺] [B(C₆F₅)₄⁻];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbonium(such as triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl,propyl, n-butyl, sec-butyl, or t-butyl).

In a preferred embodiment, any of the activators described herein may bemixed together before or after combination with the catalyst compound,preferably before being mixed with the catalyst compound.

In some embodiments two NCA activators may be used in the polymerizationand the molar ratio of the first NCA activator to the second NCAactivator can be any ratio. In some embodiments, the molar ratio of thefirst NCA activator to the second NCA activator is 0.01:1 to 10,000:1,preferably 0.1:1 to 1000:1, preferably 1:1 to 100:1.

Further, the typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is a 1:1 molar ratio. Alternate preferredranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1,alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1. Aparticularly useful range is from 0.5:1 to 10:1, preferably 1:1 to 5:1.

It is also within the scope of this invention that the catalystcompounds can be combined with combinations of alumoxanes and NCAs (see,for example, U.S. Pat. Nos. 5,153,157, 5,453,410, EP 0 573 120 B1, WO94/07928, and WO 95/14044 which discuss the use of an alumoxane incombination with an ionizing activator).

Optional Scavengers or Co-Activators

In addition to these activator compounds, scavengers or co-activatorsmay be used. Aluminum alkyl or organoaluminum compounds which may beutilized as scavengers or co-activators include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

Chain Transfer Agents

This invention further relates to methods to polymerize olefins usingthe above catalsyts in the presence of a chain transfer agent.

A “chain transfer agent” is any agent capable of hydrocarbyl and/orpolymeryl group exchange between a coordinative polymerization catalystand the metal center of the chain transfer agent during a polymerizationprocess. The chain transfer agent can be any desirable chemical compoundsuch as those disclosed in WO 2007/130306. Preferably, the chaintransfer agent is selected from Group 2, 12 or 13 alkyl or arylcompounds; preferably zinc, magnesium or aluminum alkyls or aryls;preferably where the alkyl is a C1 to C30 alkyl, alternately a C2 to C20alkyl, alternately a C3 to 12 alkyl, typically selected independentlyfrom methyl, ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl, hexyl,cyclohexyl, phenyl, octyl, nonyl, decyl, undecyl, and dodecyl; and wheredi-ethylzinc is particularly preferred.

In a particularly useful embodiment, this invention relates to acatalyst system comprising activator, catalyst compound as describedherein and chain transfer agent wherein the chain transfer agent isselected from Group 2, 12 or 13 alkyl or aryl compounds.

In a particularly useful embodiment, the chain transfer agent isselected from dialkyl zinc compounds, where the alkyl is selectedindependently from methyl, ethyl, propyl, butyl, isobutyl, tertbutyl,pentyl, hexyl, cyclohexyl, and phenyl.

In a particularly useful embodiment, the chain transfer agent isselected from trialkyl aluminum compounds, where the alkyl is selectedindependently from methyl, ethyl, propyl, butyl, isobutyl, tertbutyl,pentyl, hexyl, cyclohexyl, and phenyl.

Useful chain transfer agents are typically present at from 10 or 20 or50 or 100 equivalents to 600 or 700 or 800 or 1000 equivalents relativeto the catalyst component. Alternately the chain transfer agent (“CTA”)is preset at a catalyst complex-to-CTA molar ratio of from about 1:3000to 10:1; alternatively 1:2000 to 10:1; alternatively 1:1000 to 10:1;alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1.

Useful chain transfer agents include diethylzinc, tri-n-octyl aluminum,trimethylaluminum, triethylaluminum, tri-isobutylaluminum,tri-n-hexylaluminum, diethyl aluminum chloride, dibutyl zinc,di-n-propylzinc, di-n-hexylzinc, di-n-pentylzinc, di-n-decylzinc,di-n-dodecylzinc, di-n-tetradecylzinc, di-n-hexadecylzinc,di-n-octadecylzinc, diphenylzinc, diisobutylaluminum hydride,diethylaluminum hydride, di-n-octylaluminum hydride, dibutylmagnesium,diethylmagnesium, dihexylmagnesium, and triethylboron.

Optional Support Materials

In embodiments herein, the catalyst system may comprise an inert supportmaterial. Preferably the supported material is a porous supportmaterial, for example, talc, and inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other organic orinorganic support material and the like, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in metallocenecatalyst systems herein include Groups 2, 4, 13, and 14 metal oxides,such as silica, alumina, and mixtures thereof. Other inorganic oxidesthat may be employed either alone or in combination with the silica, oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, for example, finely dividedfunctionalized polyolefins, such as finely divided polyethylene.Particularly useful supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania, and the like. Preferredsupport materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof,more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 m. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 m. Mostpreferably the surface area of the support material is in the range isfrom about 100 to about 400 m²/g, pore volume from about 0.8 to about3.0 cc/g and average particle size is from about 5 to about 100 m. Theaverage pore size of the support material useful in the invention is inthe range of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å. In some embodiments, the support materialis a high surface area, amorphous silica (surface area=300 m²/gm; porevolume of 1.65 cm³/gm). Preferred silicas are marketed under thetradenames of DAVISON 952 or DAVISON 955 by the Davison ChemicalDivision of W.R. Grace and Company. In other embodiments DAVISON 948 isused.

The support material should be dry, that is, free of absorbed water.Drying of the support material can be effected by heating or calciningat about 100° C. to about 1000° C., preferably at least about 600° C.When the support material is silica, it is heated to at least 200° C.,preferably about 200° C. to about 850° C., and most preferably at about600° C.; and for a time of about 1 minute to about 100 hours, from about12 hours to about 72 hours, or from about 24 hours to about 60 hours.The calcined support material must have at least some reactive hydroxyl(OH) groups to produce supported catalyst systems of this invention. Thecalcined support material is then contacted with at least onepolymerization catalyst comprising at least one metallocene compound andan activator.

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a metallocene compound and an activator. Insome embodiments, the slurry of the support material is first contactedwith the activator for a period of time in the range of from about 0.5hours to about 24 hours, from about 2 hours to about 16 hours, or fromabout 4 hours to about 8 hours. The solution of the metallocene compoundis then contacted with the isolated support/activator. In someembodiments, the supported catalyst system is generated in situ. Inalternate embodiment, the slurry of the support material is firstcontacted with the catalyst compound for a period of time in the rangeof from about 0.5 hours to about 24 hours, from about 2 hours to about16 hours, or from about 4 hours to about 8 hours. The slurry of thesupported metallocene compound is then contacted with the activatorsolution.

The mixture of the metallocene, activator and support is heated to about0° C. to about 70° C., preferably to about 23° C. to about 60° C.,preferably at room temperature. Contact times typically range from about0.5 hours to about 24 hours, from about 2 hours to about 16 hours, orfrom about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator, and the metallocene compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

Polymerization Processes

In embodiments herein, the invention relates to polymerization processeswhere monomer (such as propylene), and optionally comonomer, arecontacted with a catalyst system comprising an activator and at leastone metallocene compound, as described above. The catalyst compound andactivator may be combined in any order, and are combined typically priorto contacting with the monomer.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, preferably C₂ to C₂₀ alpha olefins, preferably C₂ to C₁₂alpha olefins, preferably ethylene, propylene, butene, pentene, hexene,heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.In a preferred embodiment of the invention, the monomer comprisespropylene and an optional comonomers comprising one or more of ethyleneor C₄ to C₄₀ olefins, preferably C₄ to C₂₀ olefins, or preferably C₆ toC₁₂ olefins. The C₄ to C₄₀ olefin monomers may be linear, branched, orcyclic. The C₄ to C₄₀ cyclic olefins may be strained or unstrained,monocyclic or polycyclic, and may optionally include heteroatoms and/orone or more functional groups. In another preferred embodiment, themonomer comprises ethylene and an optional comonomers comprising one ormore C₃ to C₄₀ olefins, preferably C₄ to C₂₀ olefins, or preferably C₆to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may be linear, branched,or cyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained,monocyclic or polycyclic, and may optionally include heteroatoms and/orone or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbomene, norbomadiene, dicyclopentadiene,cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene,7-oxanorbomene, 7-oxanorbomadiene, substituted derivatives thereof, andisomers thereof, preferably hexene, heptene, octene, nonene, decene,dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,dicyclopentadiene, norbomene, norbomadiene, and their respectivehomologs and derivatives, preferably norbornene, norbomadiene, anddicyclopentadiene.

Polymerization processes of this invention can be carried out in anymanner known in the art. Any suspension, homogeneous, bulk, solution(including supercritical), slurry, or gas phase polymerization processknown in the art can be used. Such processes can be run in a batch,semi-batch, or continuous mode. Homogeneous polymerization processes andslurry processes are preferred. (A homogeneous polymerization process isdefined to be a process where at least 90 wt % of the product is solublein the reaction media.) A bulk homogeneous process is particularlypreferred. (A bulk process is typically a process where monomerconcentration in all feeds to the reactor is 70 volume % or more.)Alternately, no solvent or diluent is present or added in the reactionmedium, (except for the small amounts used as the carrier for thecatalyst system or other additives, or amounts typically found with themonomer; e.g., propane in propylene). In another embodiment, the processis a slurry process. As used herein the term “slurry polymerizationprocess” means a polymerization process where a supported catalyst isemployed and monomers are polymerized on the supported catalystparticles. At least 95 wt % of polymer products derived from thesupported catalyst are in granular form as solid particles (notdissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene,and xylene. Suitable solvents also include liquid olefins which may actas monomers or comonomers including ethylene, propylene, 1-butene,1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene,1-decene, and mixtures thereof. In a preferred embodiment, aliphatichydrocarbon solvents are used as the solvent, such as isobutane, butane,pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, andmixtures thereof; cyclic and alicyclic hydrocarbons, such ascyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, andmixtures thereof. In another embodiment, the solvent is not aromatic,preferably aromatics are present in the solvent at less than 1 wt %,preferably less than 0.5 wt %, preferably less than 0 wt % based uponthe weight of the solvents.

In a preferred embodiment, the feed concentration of the monomers andcomonomers for the polymerization is 60 vol % solvent or less,preferably 40 vol % or less, or preferably 20 vol % or less, based onthe total volume of the feedstream. Preferably the polymerization is runin a bulk process.

Preferred polymerizations can be run at any temperature and/or pressuresuitable to obtain the desired polymers. Typical temperatures and/orpressures include a temperature in the range of from about 0° C. toabout 300° C., preferably about 20° C. to about 200° C., preferablyabout 35° C. to about 150° C., preferably from about 40° C. to about120° C., preferably from about 70° C. to about 120° C., preferably fromabout 80° C. to about 120° C., preferably from about 90° C. to about120° C., preferably from about 95° C. to about 110° C.; and at apressure in the range of from about 0.35 MPa to about 10 MPa, preferablyfrom about 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa toabout 4 MPa.

In a typical polymerization, the run time of the reaction is up to 300minutes, preferably in the range of from about 5 to 250 minutes, orpreferably from about 10 to 120 minutes.

In another embodiment of the invention, the polymerization temperatureis preferably from about 70° C. to about 130° C., preferably from about80° C. to about 125° C., preferably from about 90° C. to about 120° C.,preferably from about 95° C. to about 110° C. and the polymerizationprocess is a homogeneous process, preferably a solution process.

In some embodiments hydrogen is present in the polymerization reactor ata partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferablyfrom 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig(0.7 to 70 kPa). In some embodiments hydrogen is not added thepolymerization reactor, i.e. hydrogen may be present from other sources,such as a hydrogen generating catalyst, but none is added to thereactor.

In an embodiment of the invention, the activity of the catalyst is atleast 50 g/mmol/hour, preferably 500 g/mmol/hour or more, preferably5000 g/mmol/hr or more, preferably 50,000 g/mmol/hr or more, preferably100,000 g/mmol/hr or more, preferably 150,000 g/mmol/hr or more,preferably 200,000 g/mmol/hr or more, preferably 250,000 g/mmol/hr ormore, preferably 300,000 g/mmol/hr or more, preferably 350,000 g/mmol/hror more. In an alternate embodiment, the conversion of olefin monomer isat least 10%, based upon polymer yield and the weight of the monomerentering the reaction zone, preferably 20% or more, preferably 30% ormore, preferably 50% or more, preferably 80% or more.

In a preferred embodiment, little or no scavenger is used in the processto produce the ethylene polymer. Preferably, scavenger (such as trialkyl aluminum) is present at zero mol %, alternately the scavenger ispresent at a molar ratio of scavenger metal to transition metal of lessthan 100:1, preferably less than 50:1, preferably less than 15:1,preferably less than 10:1.

In a preferred embodiment, the polymerization: 1) is conducted attemperatures of 0 to 300° C. (preferably 90 to 150° C., preferably 95 to120° C.); 2) is conducted at a pressure of atmospheric pressure to 10MPa (preferably 0.35 to 10 MPa, preferably from 0.45 to 6 MPa,preferably from 0.5 to 4 MPa); 3) is conducted in an aliphatichydrocarbon solvent (such as isobutane, butane, pentane, isopentane,hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof;cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof; preferablywhere aromatics are preferably present in the solvent at less than 1 wt%, preferably less than 0.5 wt %, preferably at 0 wt % based upon theweight of the solvents); 4) the polymerization preferably occurs in onereaction zone; 5) the productivity of the catalyst compound is at least80,000 g/mmol/hr (preferably at least 150,000 g/mmol/hr, preferably atleast 200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr,preferably at least 300,000 g/mmol/hr); 6) optionally scavengers (suchas trialkyl aluminum compounds) are absent (e.g., present at zero mol %,alternately the scavenger is present at a molar ratio of scavenger metalto transition metal of less than 100:1, preferably less than 50:1,preferably less than 15:1, preferably less than 10:1); and 7) optionallyhydrogen is present in the polymerization reactor at a partial pressureof 0.001 to 50 psig (0.007 to 345 kPa) (preferably from 0.01 to 25 psig(0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)). In apreferred embodiment, the catalyst system used in the polymerizationcomprises no more than one catalyst compound. A “reaction zone” alsoreferred to as a “polymerization zone” is a vessel where polymerizationtakes place, for example a batch reactor. When multiple reactors areused in either series or parallel configuration, each reactor isconsidered as a separate polymerization zone. For a multi-stagepolymerization in both a batch reactor and a continuous reactor, eachpolymerization stage is considered as a separate polymerization zone. Ina preferred embodiment, the polymerization occurs in one reaction zone.Room temperature is 23° C. unless otherwise noted.

Other additives may also be used in the polymerization, as desired, suchas one or more scavengers, promoters, modifiers, chain transfer agents(such as diethyl zinc), reducing agents, oxidizing agents, hydrogen,aluminum alkyls, or silanes.

In particularly useful embodiments, this invention relates to a processto polymerize olefins comprising: 1) contacting, at a temperature of 60°C. or more (alternately 80° C. or more, alternately 90° C. or more,alternately 95° C. or more), one or more olefins with the catalystsystem described herein (preferably the catalyst compound is present ina rac:meso ratio of at least 7:1); and 2) obtaining polymer having ag′vis of 0.97 or less (alternately 0.95 or less, alternately 0.90 orless) and an Mw of 200,000 g/mol or more, as determined by GPC-DRI(Alternately 300,000 g/mol or more, alternately 400,000 g/mol or more).

Preferably, the process occurs at a temperature of from about 90° C. toabout 200° C., at a pressure in the range of from about 0.35 MPa toabout 10 MPa, and at a time up to 300 minutes in the solution slurry orgas phase.

Preferably when the polymer produced by the process herein has anethylene content of 10%, the polymer also has an Mw that is ≥0.9 timesthe Mw of a propylene ethylene copolymer having 40 wt % ethyleneproduced at the under the same polymerization conditions (except forethylene and propylene monomer concentrations) using the same catalystsystem and both Mw's are 200,000 g/mol (GPC-DRI) or more.

In a particularly preferred embodiment, this invention relates to aprocess to polymerize olefins comprising: 1) contacting, at atemperature of 95° C. or more, ethylene and propylene with a catalystsystem described herein; 2) obtaining polymer having: a) from 0 to 20weight % ethylene, based upon the weight of the copolymer; b) an Mw of50,000 g/mol or more (preferably 200,000 g/mol or more), as determinedby GPC-DRI; c) a melting point of X° C. or more, where X=(the Tm of thepolymer made under the same conditions except that the polymerizationtemperature is 70° C.) minus 10° C., and optionally the polymer has anMw that is ≥0.9 times the Mw of a propylene ethylene copolymer having 40wt % ethylene produced at the under the same polymerization conditions(except for ethylene and propylene monomer concentrations) using thesame catalyst system, the propylene ethylene copolymer having 40 wt %ethylene has an Mw of 200,000 g/mol (GPC-DRI) or more.

Gas Phase Polymerization

Generally, in a fluidized gas phase process for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream is withdrawn from the fluidized bed andrecycled back into the reactor. Simultaneously, polymer product iswithdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. Illustrative gas phase polymerization processes canbe as discussed and described in U.S. Pat. Nos. 4,543,399; 4,588,790;5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471;5,462,999; 5,616,661; and 5,668,228.

The reactor pressure in a gas phase process can vary from about 69 kPato about 3,450 kPa, about 690 kPa to about 3,450 kPa, about 1,380 kPa toabout 2,759 kPa, or about 1,724 kPa to about 2,414 kPa.

The reactor temperature in the gas phase process can vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 65° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. In anotherembodiment, when high density polyethylene is desired the reactortemperature is typically between about 70° C. and about 105° C.

The productivity of the catalyst or catalyst system in a gas phasesystem is influenced by the partial pressure of the main monomer. Thepreferred mole percent of the main monomer, ethylene or propylene,preferably ethylene, is from about 25 mol % to about 90 mol % and thecomonomer partial pressure is from about 138 kPa to about 5,000 kPa,preferably about 517 kPa to about 2,069 kPa, which are typicalconditions in a gas phase polymerization process. Also in some systemsthe presence of comonomer can increase productivity.

In a preferred embodiment, the reactor can be capable of producing morethan 227 kilograms polymer per hour (kg/hr) to about 90,900 kg/hr orhigher, preferably greater than 455 kg/hr, more preferably greater than4,540 kg/hr, even more preferably greater than 11,300 kg/hr, still morepreferably greater than 15,900 kg/hr, still even more preferably greaterthan 22,700 kg/hr, and preferably greater than 29,000 kg/hr to greaterthan 45,500 kg/hr, and most preferably over 45,500 kg/hr.

The polymerization in a stirred bed can take place in one or twohorizontal stirred vessels according to the polymerization mode. Thereactors can be subdivided into individuallygas-composition-controllable and/orpolymerization-temperature-controllable polymerization compartments.With continuous catalyst injection, essentially at one end of thereactor, and powder removal at the other end, the residence timedistribution approaches that of plug flow reactor. Preferably thefluorocarbon, if present, is introduced into the first stirred vessel.

Other gas phase processes contemplated by the processes discussed anddescribed herein can include those described in U.S. Pat. Nos.5,627,242; 5,665,818; 5,677,375; EP-A-0 794 200; EP-A-0 802 202; andEP-B-634 421.

In another preferred embodiment the catalyst system is in liquid,suspension, dispersion, and/or slurry form and can be introduced intothe gas phase reactor into a resin particle lean zone. Introducing aliquid, suspension, dispersion, and/or slurry catalyst system into afluidized bed polymerization into a particle lean zone can be asdiscussed and described in U.S. Pat. No. 5,693,727.

In some embodiments, the gas phase polymerization can operate in theabsence of fluorocarbon. In some embodiments, the gas phasepolymerization can be conducted in the presence of a fluorocarbon.Generally speaking the fluorocarbons can be used as polymerization mediaand/or as condensing agents.

Slurry Phase Polymerization

A slurry polymerization process generally operates at a pressure rangebetween about 103 kPa to about 5,068 kPa or even greater and atemperature from about 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which monomer and comonomersalong with catalyst are added. The suspension including diluent isintermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane mediumhaving from about 3 to about 7 carbon atoms, preferably a branchedalkane. The medium employed can be liquid under the conditions ofpolymerization and relatively inert. When a propane medium is used theprocess can be operated above the reaction diluent critical temperatureand pressure. Preferably, a hexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique, referred to asa particle form polymerization or a slurry process, can includemaintaining the temperature below the temperature at which the polymergoes into solution. Such technique is well known in the art, and can beas discussed and described in U.S. Pat. No. 3,248,179. The preferredtemperature in the particle form process can be from about 20° C. toabout 110° C. Two preferred polymerization processes for the slurryprocess can include those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processescan be as discussed and described in U.S. Pat. No. 4,613,484.

In another embodiment, the slurry process can be carried outcontinuously in a loop reactor. The catalyst, as a slurry in mineral oiland/or paraffinic hydrocarbon or as a dry, free flowing powder, can beinjected regularly to the reactor loop, which can be filled with acirculating slurry of growing polymer particles in a diluent containingmonomer and comonomer. Hydrogen, optionally, can be added as a molecularweight control. The reactor can be operated at a pressure of about 3,620kPa to about 4,309 kPa and at a temperature from about 60° C. to about115° C. depending on the desired polymer melting characteristics.Reaction heat can be removed through the loop wall since much of thereactor is in the form of a double-jacketed pipe. The slurry is allowedto exit the reactor at regular intervals or continuously to a heated lowpressure flash vessel, rotary dryer, and a nitrogen purge column insequence for removal of the diluent and at least a portion of anyunreacted monomer and/or comonomers. The resulting hydrocarbon freepowder can be compounded for use in various applications.

The reactor used in the slurry process can produce greater than 907kg/hr, more preferably greater than 2,268 kg/hr, and most preferablygreater than 4,540 kg/hr polymer. In another embodiment the slurryreactor can produce greater than 6,804 kg/hr, preferably greater than11,340 kg/hr to about 45,500 kg/hr. The reactor used in the slurryprocess can be at a pressure from about 2,758 kPa to about 5,516 kPa,preferably about 3,103 kPa to about 4,827 kPa, more preferably fromabout 3,448 kPa to about 4,482 kPa, most preferably from about 3,620 kPato about 4,309 kPa.

The concentration of the predominant monomer in the reactor liquidmedium in the slurry process can be from about 1 wt % to about 30 wt %,preferably from about 2 wt % to about 15 wt %, more preferably fromabout 2.5 wt % to about 10 wt %, most preferably from about 3 wt % toabout 20 wt %.

In one or more embodiments, the slurry and/or gas phase polymerizationcan be operated in the absence of or essentially free of any scavengers,such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum andtri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and thelike. Operation of the slurry and/or gas phase reactors in the absenceor essentially free of any scavengers can be as discussed and describedin WO 96/08520 and U.S. Pat. No. 5,712,352. In another embodiment thepolymerization processes can be run with scavengers. Typical scavengersinclude trimethyl aluminum, tri-ethyl aluminum, tri-isobutyl aluminum,tri-n-octyl aluminum, and an excess of alumoxane and/or modifiedalumoxane.

In some embodiments, the slurry phase polymerization can operate in theabsence of a fluorocarbon. In some embodiments, the slurry phasepolymerization can be conducted in the presence of a fluorocarbon.Generally speaking the fluorocarbons can be used as polymerizationmedia.

Solution Phase Polymerization

As used herein, the phrase “solution phase polymerization” refers to apolymerization system where the polymer produced is soluble in thepolymerization medium. Generally this involves polymerization in acontinuous reactor in which the polymer formed and the starting monomerand catalyst materials supplied, are agitated to reduce or avoidconcentration gradients and in which the monomer acts as a diluent orsolvent or in which a hydrocarbon is used as a diluent or solvent.Suitable processes typically operate at temperatures from about 0° C. toabout 250° C., preferably from about 50° C. to about 200° C., preferablyfrom about 80° C. to about 150° C., more preferably from about 90° C. toabout 140° C., more preferably from about 95° C. to about 120° C. and atpressures of about 0.1 MPa or more, preferably 2 MPa or more. The upperpressure limit is not critically constrained but typically can be about200 MPa or less, preferably, 120 MPa or less. Temperature control in thereactor can generally be obtained by balancing the heat ofpolymerization and with reactor cooling by reactor jackets or coolingcoils to cool the contents of the reactor, auto refrigeration,pre-chilled feeds, vaporization of liquid medium (diluent, monomers orsolvent) or combinations of all three. Adiabatic reactors withpre-chilled feeds can also be used. The purity, type, and amount ofsolvent can be optimized for the maximum catalyst productivity for aparticular type of polymerization. The solvent can be also introduced asa catalyst carrier. The solvent can be introduced as a gas phase or as aliquid phase depending on the pressure and temperature. Advantageously,the solvent can be kept in the liquid phase and introduced as a liquid.Solvent can be introduced in the feed to the polymerization reactors.

In a preferred embodiment, the polymerization process can be describedas a continuous, non-batch process that, in its steady state operation,is exemplified by removal of amounts of polymer made per unit time,being substantially equal to the amount of polymer withdrawn from thereaction vessel per unit time. By “substantially equal” we intend thatthese amounts, polymer made per unit time, and polymer withdrawn perunit time, are in ratios of one to other, of from 0.9:1; or 0.95:1; or0.97:1; or 1:1. In such a reactor, there will be a substantiallyhomogeneous monomer distribution.

Preferably in a continuous process, the mean residence time of thecatalyst and polymer in the reactor generally can be from about 5minutes to about 8 hours, and preferably from about 10 minutes to about6 hours, more preferably from 10 minutes to 1 hour. In some embodiments,comonomer (such as ethylene) can be added to the reaction vessel in anamount to maintain a differential pressure in excess of the combinedvapor pressure of the main monomer (such as a propylene) and anyoptional diene monomers present.

In another embodiment, the polymerization process can be carried out ata pressure of ethylene of from about 68 kPa to about 6,800 kPa, mostpreferably from about 272 to about 5,440 kPa). The polymerization isgenerally conducted at a temperature of from about 25° C. to about 250°C., preferably from about 75° C. to about 200° C., and most preferablyfrom about 95° C. to about 200° C.

The addition of a small amount of hydrocarbon to a typical solutionphase process can cause the polymer solution viscosity to drop and orthe amount of polymer solute to increase. Addition of a larger amount ofsolvent in a traditional solution process can cause the separation ofthe polymer into a separate phase (which can be solid or liquid,depending on the reaction conditions, such as temperature or pressure).

The processes discussed and described herein can be carried out incontinuous stirred tank reactors, batch reactors, or plug flow reactors.One reactor can be used even if sequential polymerizations are beingperformed, preferably as long as there is separation in time or space ofthe two reactions. Likewise two or more reactors operating in series orparallel can also be used. These reactors can have or not have internalcooling and the monomer feed may or may not be refrigerated. See thegeneral disclosure of U.S. Pat. No. 5,001,205 for general processconditions. See also, WO 96/33227 and WO 97/22639.

Supercritical or Supersolution Polymerization

In aspects of the invention, the processes and or catalyst compositionsdisclosed herein may be used in a supercritical or super solution phase.A supercritical polymerization means a polymerization process in whichthe polymerization system is in a dense fluid (i.e., its density is 300kg/m³ or higher), supercritical state. The terms “dense fluid” and“supercritical state” are defined in U.S. Pat. No. 7,812,104. A supersolution polymerization is one where the polymerization occurs at atemperature of 65° C. to 150° C., preferably from about 75° C. to about140° C., preferably from about 90° C. to about 140° C., more preferablyfrom about 100° C. to about 140° C., and at pressures of between 1.72MPa and 35 MPa, preferably between 5 and 30 MPa. For further informationon supercritical and super solution polymerizations, please see U.S.Pat. Nos. 7,812,104; 8,008,412; 7,812,104; 9,249,239; 7,729,536;8,058,371; and US 2008/0153997.

Polyolefin Products

This invention also relates to compositions of matter produced by themethods described herein.

In a preferred embodiment, the process described herein producespropylene homopolymers or propylene copolymers, such aspropylene-ethylene and/or propylene-alphaolefin (preferably C₃ to C₂₀)copolymers (such as propylene-hexene copolymers or propylene-octenecopolymers), preferably having: a Mw/Mn of greater than 1 to 4(preferably greater than 1 to 3).

Likewise, the process of this invention produces olefin polymers,preferably polyethylene and polypropylene homopolymers and copolymers.In a preferred embodiment, the polymers produced herein are homopolymersof ethylene or propylene, are copolymers of ethylene preferably havingfrom 0 to 50 mole % (alternately from 0.5 to 25 mole %, alternately from0.5 to 20 mol %, alternately from 1 to 15 mole %, preferably from 3 to10 mole %) of one or more C₃ to C₂₀ olefin comonomer (preferably C₃ toC₁₂ alpha-olefin, preferably propylene, butene, hexene, octene, decene,dodecene, preferably propylene, butene, hexene, octene), or arecopolymers of propylene preferably having from 0 to 25 mole %(alternately from 0.5 to 20 mole %, alternately from 1 to 15 mole %,preferably from 3 to 10 mole %) of one or more of C₂ or C₄ to C₂₀ olefincomonomer (preferably ethylene or C₄ to C₁₂ alpha-olefin, preferablyethylene, butene, hexene, octene, decene, dodecene, preferably ethylene,butene, hexene, octene).

In a preferred embodiment, the monomer is ethylene and the comonomer ishexene, preferably from 1 to 15 mole % hexene, alternately 1 to 10 mole%.

In a preferred embodiment, the monomer is propylene and the comonomer isethylene, preferably from 0.5 to 99.5 wt % ethylene, alternately 1 to 65wt % ethylene, alternately 1 to 60 wt % ethylene, alternately 2 to 50 wt% ethylene, alternately 3 to 30 wt % ethylene, alternately 4 to 20 wt %ethylene, based upon the weight of the copolymer.

Typically, the polymers produced herein have an Mw (as measured byGPC-DRI) from 5,000 to 1,000,000 g/mol, alternately from 200,000 to1,000,000 g/mol, alternately 250,000 to 800,000 g/mol, alternately300,000 to 600,000 g/mol, alternately from 300,000 to 500,000 g/mol.

Typically, the polymers produced herein have an Mw/Mn (as measured byGPC-DRI) of greater than 1 to 40, preferably 1 to 20, preferably 1.1 to15, preferably 1.2 to 10, preferably 1.3 to 5, preferably 1.4 to 4.

Typically, the polymers produced herein (typically propylene-ethylenecopolymers) have an Mw (as measured by GPC-DRI) of 5,000 to 1,000,000g/mol (preferably 200,000 to 750,000 g/mol, preferably 250,000 to500,000 g/mol, preferably 250,000 to 300,000 g/mol, preferably 250,000to 350,000 g/mol), and/or an Mw/Mn of greater than 1 to 40 (alternately1.1 to 20, alternately 1.2 to 10, alternately 1.3 to 5, 1.4 to 4,alternately 1.4 to 3).

In a preferred embodiment the polymer produced herein has a unimodal ormultimodal molecular weight distribution as determined by Gel PermeationChromatography (GPC). By “unimodal” is meant that the GPC trace has onepeak or inflection point. By “multimodal” is meant that the GPC tracehas at least two peaks or inflection points. An inflection point is thatpoint where the second derivative of the curve changes in sign (e.g.,from negative to positive or vice versus).

The polymer produced herein can have a melting point (Tm, DSC peaksecond melt) of at least 145° C., or at least 150° C., or at least 152°C., or at least 153° C., or at least 154° C. For example, the polymercan have a melting point from at least 145° C. to about 175° C., about150° C. to about 165° C., about 152° C. to about 160° C.

The polymer produced herein can have a 1% secant flexural modulus from alow of about 1100 MPa, about 1200 MPa, about 1250 MPa, about 1300 MPa,about 1400 MPa, or about 1,500 MPa to a high of about 1,800 MPa, about2,100 MPa, about 2,600 MPa, or about 3,000 MPa, as measured according toASTM D 790 (A, 1.0 mm/min). For example, the polymer can have a flexuralmodulus from about 1100 MPa to about 2,200 MPa, about 1200 MPa to about2,000 MPa, about 1400 MPa to about 2,000 MPa, or about 1500 MPa or more,as measured according to ASTM D 790 (A, 1.0 mm/min).

The polymer produced herein can have a melt flow rate (MFR, ASTM 1238,2.16 kg, 230° C.) from a low of about 0.1 dg/min, about 0.2 dg/min,about 0.5 dg/min, about 1 dg/min, about 15 dg/min, about 30 dg/min, orabout 45 dg/min to a high of about 75 dg/min, about 100 dg/min, about200 dg/min, or about 300 dg/min.

The polymer produced herein can have a branching index (g′vis) of 0.95or less, preferably 0.93 or less, preferably 0.90 or less, preferably0.88 or less.

Interestingly, the polymers produced herein have high Mw at both higherand lower comonomer incorporation. For example see FIG. 3, whereCatalysts A, B and C show that the polymers with lower ethylene contenthave Mw's that are near the Mw's of copolymers made with the samecatalyst having higher ethylene content.

In an embodiment of the invention, the polymer produced herein is apropylene ethylene copolymer having an ethylene content of 10 to lessthan 40 wt % mol or wt %) and an Mw that is ≥0.9 (alternately 1.0,alternately 1.1, alternately 1.25, alternately 1.5) times the Mw of apropylene ethylene copolymer having 40 wt % ethylene produced at theunder the same polymerization conditions (except for ethylene monomerconcentration) using the same catalyst system and both Mw's are 200,000g/mol (GPC-DRI) or more, preferably 250,000 g/mol or more, preferably300,000 g/mol or more, preferably 350,000 g/mol or more.

Advantageously, the polymer produced is a propylene ethylene copolymerhaving an Mw that is ≥0.9 times (alternately 1.0 times) the Mw of apropylene ethylene copolymer having 40 wt % ethylene produced at theunder the same polymerization conditions (except for ethylene andpropylene monomer concentrations) using the same catalyst system,preferably the Mw is 200,000 g/mol (GPC-DRI) or more.

In an embodiment of the invention, any polymer produced herein at apolymerization temperature of 80° C. or more (preferably at 90° C. ormore, preferably 95° C. or more, preferably at 100° C. or more) has amelting point of X° C. or more (alternately X° C.+1° C. or more,alternately X° C.+2° C. or more, alternately X° C.+3° C. or more,alternately X° C.+4° C. or more, alternately X° C.+5° C. or more,alternately X° C.+6° C. or more, alternately X° C.+7° C. or more) whereX=(the Tm of the polymer made under the same conditions except that thepolymerization temperature is 70° C.) minus 10° C. For example if the Tmof the polymer made at 70° C. is 155° C., then the Tm of the polymermade at 80° C. or more, is 145° C. or more.

Blends

In another embodiment, the polymer (preferably the polyethylene orpolypropylene) produced herein is combined with one or more additionalpolymers prior to being formed into a film, molded part or otherarticle. Other useful polymers include polyethylene, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene, and/orbutene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE,HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, cross linkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, polyacetal,polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

In a preferred embodiment, the polymer (preferably the polyethylene orpolypropylene) is present in the above blends, at from 10 to 99 wt %,based upon the weight of the polymers in the blend, preferably 20 to 95wt %, even more preferably at least 30 to 90 wt %, even more preferablyat least 40 to 90 wt %, even more preferably at least 50 to 90 wt %,even more preferably at least 60 to 90 wt %, even more preferably atleast 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of theinvention with one or more polymers (as described above), by connectingreactors together in series to make reactor blends or by using more thanone catalyst in the same reactor to produce multiple species of polymer.The polymers can be mixed together prior to being put into the extruderor may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such asIRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites(e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

Specifically, any of the foregoing polymers, such as the foregoingpolypropylenes or blends thereof, may be used in a variety of end-useapplications. Such applications include, for example, mono- ormulti-layer blown, extruded, and/or shrink films. These films may beformed by any number of well-known extrusion or coextrusion techniques,such as a blown bubble film processing technique, wherein thecomposition can be extruded in a molten state through an annular die andthen expanded to form a uni-axial or biaxial orientation melt prior tobeing cooled to form a tubular, blown film, which can then be axiallyslit and unfolded to form a flat film. Films may be subsequentlyunoriented, uniaxially oriented, or biaxially oriented to the same ordifferent extents. One or more of the layers of the film may be orientedin the transverse and/or longitudinal directions to the same ordifferent extents. The uniaxially orientation can be accomplished usingtypical cold drawing or hot drawing methods. Biaxial orientation can beaccomplished using tenter frame equipment or a double bubble processesand may occur before or after the individual layers are broughttogether.

For example, a polyethylene layer can be extrusion coated or laminatedonto an oriented polypropylene layer or the polyethylene andpolypropylene can be coextruded together into a film then oriented.Likewise, oriented polypropylene could be laminated to orientedpolyethylene or oriented polyethylene could be coated onto polypropylenethen optionally the combination could be oriented even further.Typically the films are oriented in the Machine Direction (MD) at aratio of up to 15, preferably between 5 and 7, and in the TransverseDirection (TD) at a ratio of up to 15, preferably 7 to 9. However, inanother embodiment the film is oriented to the same extent in both theMD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 μm are usually suitable.Films intended for packaging are usually from 10 to 50 μm thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

In another embodiment, one or more layers may be modified by coronatreatment, electron beam irradiation, gamma irradiation, flametreatment, or microwave. In a preferred embodiment, one or both of thesurface layers is modified by corona treatment.

Experimental

MAO is methyl alumoxane (30 wt % in toluene) obtained from Albemarle.

TONAL is tri-n-octyl aluminum.

Me₂Si(2-iPr,4-3′5′di-t-BuPhInd)(2-Me,4-2Ph-PhInd)ZrCl₂ andMe₂Si(2-iPr,4-3′5′di-t-BuPhInd)(2-Me,4-4-3′5′di-t-BuPhInd)ZrCl₂ areproduced as described in US 2015/0025208.

MCN1 is dimethylsilyl (4-oPh.2.-2-n-hexyl-indenyl)(2-methyl-4-(3′,5′-di-tert-butyl-4′-methoxy-phenyl)-indenyl) zirconiumdichloride.

MCN2 is dimethylsilyl bis(4-oPh. 2.-2-n-hexyl-indenyl) zirconiumdichloride.

MCN3 is dimethylsilyl bis(4-oPh. 2.-2-n-butyl-indenyl) zirconiumdichloride.

MCN4 is dimethylsilyl (4-oPh.2.-2-n-butyl-indenyl)(2-methyl-4-(3′,5′-di-tert-butyl-4′-methoxy-phenyl)-indacenyl) zirconiumdichloride.

MCN5 is dimethylsilyl (4-oPh. 2.-2-c-propyl-indenyl)(2-methyl-4-(3′,5′-di-tert-butyl-4′-methoxy-phenyl)-indenyl) zirconiumdichloride.

MNC6 is dimethylsilyl (4-oPh. 2.-2-c-propyl-indenyl)(2-methyl-4-(3′,5′-di-tert-butyl-phenyl)-indenyl) zirconium dichloride.

MCN7 is dimethylsilyl (4-oPh.2.-2-methyl-indenyl)(2-isopropyl-4-(3′,5′-di-tert-butyl-4′-methoxy-phenyl)-indenyl)zirconium dichloride.

MCN8 is dimethylsilyl bis(2-c-propyl-4-(3′,5′-di-tert-butyl-phenyl)-indenyl) zirconiumdichloride.

MCN9 is dimethylsilylbis(2-methyl-4-(3′,5′-di-tert-butyl-4′-methoxy-phenyl)-indenyl)zirconium dichloride.

MCN10 is dimethylsilyl (4(4′-tert-butyl-phenyl)-2-methyl-indenyl)(2-isopropyl-4-(4′-tert-butyl-phenyl)-indenyl) zirconium dimethyl.

MCN11 is dimethylsilyl (4-phenyl-2-methyl-indacenyl)(2-isopropyl-4-(4-tert-butyl-phenyl)-indenyl) zirconium dimethyl.

MCN12 is dimethylsilyl bis(4-phenyl-2-n-butyl-indenyl) zirconiumdichloride (6:1 rac:meso ratio).

MCN13 is dimethylsilyl bis(4-phenyl-2-n-butyl-indenyl) zirconiumdichloride (1:2 rac:meso ratio).

MCN14 is dimethylsilyl (4-oPh.2.-2-n-hexyl-indenyl)(2-methyl-4-(3′,5′-di-tert-butyl-4′-methoxy-phenyl)-indenyl) zirconiumdimethyl.

Catalyst A is MCN1 supported on SMAO.

Catalyst B is MCN2 supported on SMAO.

Catalyst C is MCN3 supported on SMAO.

Catalyst D (Comparative) is MCN8 supported on SMAO.

Catalyst E (Comparative) is MCN10 supported on SMAO.

Catalyst F (Comparative) is MCN9 supported on SMAO.

Metallocene Synthesis:

MCN1

4-([1,1′-Biphenyl]-2-yl)-2-^(n)Hex-1H-indene

A solution of compound 4-([1,1′-Biphenyl]-2-yl)-2-bromo-1H-indene (15 g,43.2 mmol, 1 equiv.) and anhydrous toluene (150 mL) was treated withbis(triphenylphosphine)palladium(II)-dichloride (3.5 g, 4.3 mmol, 0.1equiv.). After stirring for 10 minutes, 2 M hexylmagnesium bromide indiethyl ether (112 mL, 224.6 mmol, 5.2 equiv.) was added dropwise. Thereaction was heated at 60° C. for 5 hours. The reaction was cooled withan ice bath, acidified with 1NHC1 to pH 3 and extracted with ethylacetate (3×500 mL). The combined organic layers were washed withsaturated brine (800 mL), dried over sodium sulfate, and concentratedunder reduced pressure. The residue was purified over silica gel (200 g)eluting with heptanes to give compound 7 (7 g, 46% yield) as a lightyellow oil.

Lithium {1-[4-(3′,5′-di-tert-4′-methoxybutylphenyl)-2-methyl indenide]}

A precooled solution of4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-indene (15.0 g, 43.1mmol) in diethyl ether (200 mL) was treated with nBuLi (2.5 M in hexane,18.1 mL, 45.3 mmol). The reaction was stirred at room temperature for 15h. Then all volatiles were evaporated. The residue was washed withpentane (10 mL) and dried under vacuum to yield a white solid (15.15 g).

Chlorodimethyl[4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl-indenyl] silane

A precooled solution of lithium1-[4-(3,5-di-tert-4-methoxybutylphenyl)-2-methyl indenide](15.1 g, 42.8mmol) in diethyl ether (100 mL) was treated with Me₂SiCl₂ (27.4 g, 214.0mmol), and the white slurry was stirred at room temperature for 5 h. Allvolatiles were evaporated under reduced pressure. The residue wasextracted with hexane (100 mL×2), and the combined filtrate wasconcentrated to dryness under vacuum to give white foam (18.36 g).

Dimethylsilyl[4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl-indenyl]trifluoromethane-sulfonate

A solution ofchlorodimethyl[4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-indenyl]silane(18.34 g, 41.7 mmol) in toluene (100 mL) was treated with silvertrifluoromethanesulfonate (11.2 g, 43.8 mmol) while stirring. The whiteslurry was stirred at room temperature for 5 h. Toluene was removedunder vacuum and the residue was extracted with hexane (100 mL×2). Thecollected filtrate was concentrated under vacuum to give colorless foamas the product (22.82 g).

Lithium [1-(4-oPh.2.)-2-hexyl-indenide]

A precooled solution of 4-oPh.2.-2-hexyl-indene (15.0 g, 42.6 mmol) indiethyl ether (100 mL) was treated with nBuLi (2.5 M in hexane, 17.9 mL,44.7 mmol). The reaction was stirred at room temperature for 3 h. Thenall volatiles were evaporated. The residue was washed with hexane (20mL×2) and dried under vacuum to yield a white solid as the product(14.21 g).

(4-oPh.2.-2-hexyl-indenyl)(4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl-indenyl)dimethylsilane

A precooled solution ofdimethylsilyl[4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-indenyl]trifluoromethanesulfonate (22.73 g, 39.2 mmol) in diethyl ether (100 mL)was treated with lithium [1-(4-oPh.2.-2-hexyl indenide)] (14.03 g, 39.2mmol). The solution was stirred at room temperature overnight. Diethylether was evaporated. The residue was purified by flash chromatography(silica gel, eluent: hexane) to give a pale yellow oil (13.24 g).

Dilithium dimethylsilyl (4-oPh.2.-2-hexyl indenide)(4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl indenide)

^(n)BuLi (2.5 M, 14.3 mL, 35.79 mmol) was added to a precooled solutionof the above product (13.20 g, 17.46 mmol) in diethyl ether (100 mL).The solution was stirred at room temperature for 3 h. All volatiles wereremoved under vacuum. The residue was washed with pentane (15 mL×2) anddried under vacuum to give the dilithium compound (12.11 g).

Dimethylsilyl (4-oPh.2.-2-hexyl indenyl)(4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl indenyl) zirconiumdichloride

A precooled solution of dilithium dimethylsilyl (4-oPh.2.-2-cyclopropylindenide) (4-(3,5-di-tert-butylphenyl)-2-methyl indenide (12.06 g, 15.7mmol) in toluene (100 mL) was treated with ZrCl₄ (3.79 g, 1.17 mmol).The mixture was stirred at room temperature overnight. The mixture wasfiltered through Celite to get rid of LiCl and evaporated to dryness.The residue was washed with hexane (50 mL) to get a solid as a mixtureof two isomers. The mixture was recrystallized toluene (20 mL, 100° C.to 40° C.) to get the corresponding meso-isomer metallocene (361 mg,ratio of rac/meso=1:22). The combined filtrate was concentrated andrecrystallized (10 mL of toluene and 5 mL of hexane, refluxed to roomtemperature) to afford mixture with rac/meso-ratio=15:1. The mixture wasfurther recrystallized (10 mL of toluene and 6 mL of hexane, refluxed toroom temperature) to obtain the rac-isomer (623 mg, ratio ofrac/meso=22:1). ¹H NMR (400 MHz, C₆D6, 23° C.), rac-form isomer: δ 8.26(dd, 1H), 7.91 (s, 2H), 7.51 (d, 1H), 7.43 (dd, 1H), 7.36-7.32 (m, 1H),7.29 (d, 1H), 7.25 (td, 1H), 7.18-7.09 (m, 5H), 6.95-6.83 (m, 5H), 6.69(dd, 1H), 3.41 (s, 3H), 2.76-2.66 (m, 1H), 2.48-2.38 (m, 1H), 1.96 (s,3H), 1.57 (s, 18H), 1.47-1.13 (m, 8H), 0.93-0.87 (m, 6H), 0.65 (s, 3H);meso-form isomer: ¹H NMR (400 MHz, C₆D6, 23° C.) δ 8.22-8.18 (m, 1H),7.90 (s, 2H), 7.38 (dd, 2H), 7.31-7.28 (m, 2H), 7.19-7.09 (m, 2H),7.05-7.71 (m, 3H), 6.96-6.78 (m, 4H), 6.75 (dd, 1H), 6.67 (s, 1H), 6.58(dd, 1H), 3.39 (s, 3H), 2.81-2.71 (m, 1H), 2.66-2.56 (m, 1H), 2.18 (s,3H), 1.54 (s, 18H), 1.40-1.12 (m, 8H), 0.91 (t, 3H), 0.81 (s, 3H), 0.76(s, 3H).

MCN2

Lithium {1-[(4-oPh.2.-2-^(n)hexyl) indenide]}

^(n)BuLi (2.5 M, 8.2 mL, 20.5 mmol) was added to a stirring precooledsolution of 4-([1,1′-Biphenyl]-2-yl)-2-^(n)Hex-1H-indene (6.55 g, 18.58mmol) in diethyl ether (100 mL). The solution was stirred at roomtemperature for 19 hours. All volatiles were evaporated. The residue wasdried under vacuum to give a crude product containing 0.08 equiv. ofEt₂O (6.07 g). The product was used without further purification.

Chlorodimethyl[4-oPh.2.-2-^(n)hexyl-indenyl]silane

Me₂SiCl₂ (10 g, 77.48 mmol) was added to a precooled solution of abovelithium salts (1.97 g, 5.40 mmol) in diethyl ether (60 mL). Additionaldiethyl ether (10 mL) was added. The white slurry was stirred at roomtemperature for 17 h. All volatiles were removed in vacuo. The residuewas extracted with hexane (50 mL once, 10 mL once) and the filtrate wasconcentrated under vacuum to give the product (2.19 g). The product wasused without further purification.

Dimethylsilyl [4-oPh.2.-2-^(n)hexyl-indenyl] trifluoromethanesulfonate

Silver trifluoromethanesulfonate (1.31 g, 5.098 mmol) was added to astirring solution of above product (2.16 g, 4.853 mmol) in toluene (25mL). Additional toluene (10 mL) was added. The slurry was stirred atroom temperature for 1 h. Toluene was removed under vacuum and theresidue was extracted with hexane (40 mL once, 10 mL once). The hexanefiltrate was concentrated under vacuum to give the product (2.55 g). Theproduct was used without further purification.

Bis(4-oPh.2.-2-^(n)hexyl-indenyl) dimethylsilane

Lithium {1-[1-[(4-oPh.2.-2-^(n)hexyl) indenide]}(Et₂O)_(0.08) (1.62 g,4.446 mmol) was added to a precooled solution ofdimethylsilyl[4-oPh.2.-2-^(n)hexyl-indenyl] trifluoromethanesulfonate(2.48 g, 4.439 mmol) in diethyl ether (40 mL). Additional diethyl ether(10 mL) was added. The reaction was stirred at room temperature for 19h. All volatiles were evaporated. The residue was extracted with hexane(50 mL once, 10 mL once) and the filtrate was concentrated under vacuumto give the crude product (3.28 g). The product was used without furtherpurification.

Dilithium dimethylsilyl bis(4-oPh.2.-2-^(n)hexyl-indenide)

nBuLi (2.5 M, 3.5 mL, 8.75 mmol) was added to a precooled solution ofthe above crude product (3.22 g) in diethyl ether (30 mL) and hexane (15mL). The solution was stirred at room temperature for 24 h. Allvolatiles were removed under vacuum. The residue was washed with hexane(20 mL twice) and dried under vacuum to give the crude productcontaining 0.54 equiv. of Et₂O (3.29 g).

Dimethylsilyl bis(4-oPh.2.-2-^(n)hexyl-indenyl) zirconium dichloride

ZrCl₄ (0.96 g, 4.119 mmol) was added to a precooled solution of theabove crude product (3.27 g) in toluene (40 mL). Additional toluene (10mL) was added. The mixture was stirred at room temperature for 18 h. Allvolatiles were removed under vacuum. The residue was extracted withhexane (60 mL once, 10 mL once). The hexane insolubles were thenextracted into toluene (40 mL once, 10 mL once). Toluene filtrates wereconcentrated to dryness under vacuum to give crude product as a rac/mesomixture in 1/1.2 ratio (1.15 g). Toluene (4 mL) and hexane (32 mL) wereadded. The slurry was heated to reflux and then was cooled back to roomtemperature. The mixture was stirred at room temperature for 3 days. Theprecipitates were separated, washed with hexane (5 mL twice) and weredried in vacuo to give a solid with rac/meso ratio of 1/1.6 (0.99 g).Further multiple fractional crystallizations from diethyl ether affordeda crude product (0.28 g) with rac/meso ratio of about 50/1 plus someinsoluble impurities. To this crude product was added CH₂Cl₂ (18 mL).The mixture was filtered and the insolubles were washed with additionalCH₂Cl₂ (18 mL once, 5 mL once). The filtrate and washings were combinedand evaporated to dryness. The solid obtained was washed with diethylether (5 mL) and dried in vacuo to afford the product (0.15 g,rac/meso=40/1). ¹H NMR (400 MHz, CD₂Cl₂, 23° C.): rac: δ 7.64 (m, 2H),7.49 (m, 2H), 7.40-7.46 (m, 6H), 7.11 (m, 2H), 7.04-7.08 (m, 10H), 6.91(m, 2H), 6.32 (s, 2H), 2.54 (m, 2H), 2.10 (m, 2H), 1.32-1.08 (m, 22H),0.88 (t, 6H).

MCN 3

Lithium [1-(4-oPh.2.)-2-butyl-indenide]

A precooled solution of 4-oPh.2.-2-butyl-indene (7.80 g, 24.1 mmol) indiethyl ether (50 mL) was treated with nBuLi (2.5 M in hexane, 10.1 mL,25.3 mmol). The reaction was stirred at room temperature for 3 h. Thenall volatiles were evaporated. The residue was washed with hexane (10mL×2) and dried under vacuum to yield an off-white solid as the product(7.09 g).

Chlorodimethyl [(4-oPh.2.)-2-butyl-indenyl] silane

A precooled solution of lithium [1-(4-oPh.2.)-2-butyl-indenide] (3.30 g,10.0 mmol) in diethyl ether (50 mL) was treated with Me₂SiCl₂ (6.50 g,50.0 mmol), and the resulting white slurry was stirred at roomtemperature overnight. All volatiles were evaporated under reducedpressure. The residue was extracted with hexane (30 mL×2), and thecombined filtrate was concentrated to dryness under vacuum to givecolorless oil (2.94 g).

Dimethylsilyl (4-oPh.2.-2-butyl-indenyl) trifluoromethanesulfonate

A solution of chlorodimethyl (4-oPh.2.-2-butyl-indenyl) silane (2.90 g,6.97 mmol) in toluene (30 mL) was treated with silvertrifluoromethanesulfonate (1.96 g, 7.67 mmol) while stirring. The whiteslurry was stirred at room temperature for 5 h. Toluene was evaporatedunder vacuum and the residue was extracted with hexane (30 mL×2). Thefiltrate was concentrated under vacuum to give colorless oil as theproduct (3.60 g).

Bis(4-oPh.2.-2-butyl-indenyl) dimethylsilane

A precooled solution of dimethylsilyl (4-oPh.2.-2-butyl-indenyl)trifluoromethanesulfonate (3.50 g, 6.60 mmol) in diethyl ether (30 mL)was treated with lithium [1-(4-oPh.2.)-2-butyl-indenide] (2.18 g, 6.60mmol). The solution was stirred for 3 hours at room temperature. Diethylether was evaporated. The residue was extracted with solvents (mixedwith 30 mL of toluene and 30 mL of hexane). The combined filtrate wasconcentrated and further dried over vacuum to get an off-white solid asthe product (3.24 g).

Dilithium dimethylsilyl bis(4-oPh.2.-2-butyl-indenide)

^(n)BuLi (2.5 M, 3.7 mL, 9.26 mmol) was added to a precooled solution ofbis(4-oPh.2.-2-butyl-indenyl) dimethylsilane (3.18 g, 4.52 mmol) indiethyl ether (30 mL). The solution was stirred at room temperature for3 h. All volatiles were removed under vacuum. The residue was washedwith hexane (10 mL×2) and dried under vacuum to give pale yellow foam(2.45 g).

Dimethylsilyl bis(4-oPh.2.-2-butyl-indenyl) zirconium dichloride

A precooled solution of dilithium dimethylsilylbis(4-oPh.2.-2-butyl-indenide) (2.37 g, 3.31 mmol) in toluene (30 mL)was treated with ZrCl₄ (0.76 g, 3.31 mmol). The mixture was stirred atroom temperature overnight. The mixture was evaporated to dryness. Theresidue was extracted with hot cyclohexane (50 mL). The combinedfiltrate was concentrated under reduced pressure and washed with hexane(20 mL) to get an orange solid as a mixture of two isomers. The mixturewas recrystallized (2 mL of toluene and 18 mL hexane, refluxed to roomtemperature) to afford mixture (520 mg, wet, ratio of rac/meso=10:1).Then the mixture was further recrystallized (1.5 mL of toluene and 13.5mL hexane, refluxed to room temperature) to afford the rac-isomer (100mg, ratio of rac/meso=68:1). ¹H NMR (400 MHz, C₆D6, 23° C.), rac-formisomer: δ 8.26-8.23 (m, 2H), 7.39 (s, 1H), 7.36 (s, 1H), 7.35 (d, 1H),7.33 (d, 1H), 7.22-7.12 (m, 4H), 7.10-7.05 (m, 6H), 6.90-6.78 (m, 8H),6.70 (dd, 2H), 2.66-2.55 (m, 2H), 2.41-2.30 (m, 2H), 1.29-1.19 (m, 4H),1.13-1.02 (m, 4H), 0.81 (t, 6H), 0.75 (s, 6H).

MCN 4

Chlorodimethyl (4-oPh.2.-2-butyl-inden-1-yl) silane

A precooled solution of lithium [1-(4-oPh.2.)-2-butyl-indenide] (3.30 g,10.0 mmol) in diethyl ether (50 mL) was treated with Me₂SiCl₂ (6.45 g,50.0 mmol), and the resulting white slurry was stirred over night atroom temperature. All volatiles were evaporated. The residue wasextracted with hexane (20 mL×2), and the combined filtrate wasconcentrated under reduced pressure to get colorless oil (3.91 g).

Dimethylsilyl (4-oPh.2.-2-butyl-inden-1-yl) trifluoromethanesulfonate

A precooled solution of chlorodimethyl (4-oPh.2.-2-butyl-inden-1-yl)silane (3.90 g, 9.4 mmol) in toluene (30 mL) was treated with silvertrifluoromethanesulfonate (2.64 g, 10.3 mmol) while stirring. The whiteslurry was stirred for 3 hours at room temperature. Toluene was removedunder reduced pressure, and the residue was extracted with hexane (20mL×2). The collected filtrate was concentrated under reduced pressure tocolorless oil as the product (4.88 g).

Lithium{4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenide}

A precooled solution of8-(3,5-di-tert-butyl-4-methoxyphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene(3.88 g, 10.0 mmol) in diethyl ether (20 mL) was treated with ^(n)BuLi(2.5 M in hexane, 4.2 mL, 10.5 mmol). The reaction was stirred overnight at room temperature. Then all volatiles were evaporated. Theresidue was washed with hexane (20 mL×2) and dried under vacuum to yieldan orange solid (3.60 g).

(4-oPh.2.-2-butyl-indenyl)(4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylsilane:

A precooled solution of dimethylsilyl (4-oPh.2.-2-butyl-inden-1-yl)trifluoromethanesulfonate (4.80 g, 9.06 mmol) in diethyl ether (30 mL)was treated with a solid of lithium1-[4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenide](3.57 g, 9.06 mmol). The solution was stirred overnight at roomtemperature. Diethyl ether was evaporated. The residue was extractedwith hexane (30 mL×2). The combined filtrate was concentrated to drynessand dried over vacuum to get colorless foam (6.70 g).

Dilithium dimethylsilyl (4-oPh.2.-2-butyl indenide)(4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenide)

^(n)BuLi (2.5 M, 7.1 mL, 17.83 mmol) was added to a precooled solutionof(4-oPh.2.-2-butyl-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylsilane (6.68 g, 8.70 mmol) in diethyl ether (50 mL). The mixturewas stirred for 3 hours at room temperature. All volatiles were removedunder reduced pressure. The residue was washed with cool hexane (30 mL)and dried under vacuum to yield an orange solid (6.247 g).

Dimethylsilyl (4-oPh.2.-2-butyl indenyl)(4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenyl)zirconium dichloride

A precooled solution of dilithium dimethylsilyl (4-oPh.2.-2-butylindenide)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacenide)(6.20 g, 7.95 mmol) in toluene (50 mL) was treated with a powder ofZrCl₄ (1.83 g, 7.95 mmol). The mixture was stirred for 5 hours at roomtemperature. Then the mixture was concentrated under reduced pressure,and the residue was extracted with solvents (mixed with 25 mL of tolueneand 20 mL of hexane). The combined filtrate was concentrated. Theresulting residue was recrystallized (10 mL of toluene and 50 mL ofhexane, refluxed to room temperature). Then the collected solid wasfurther recrystallized (30 mL of toluene, refluxed to room temperature)to get the meso-isomer (853 mg, ratio of rac/meso <1:100). The filtratefrom the first recrystallization was concentrated and the residue wasrecrystallized (10 mL of toluene and 50 mL of hexane, refluxed to roomtemperature) to afford rac-isomer (351 mg, ratio of rac/meso=39:1). ¹HNMR (400 MHz, C₆D6, 23° C.), meso-form isomer: δ 8.23-8.17 (m, 1H), 7.83(bs, 1H), 7.52 (d, 1H), 7.38 (s, 1H), 7.32-7.28 (m, 1H), 7.22-7.10 (m,3H), 7.07-7.03 (m, 2H), 6.97 (dd, 1H), 6.88-6.77 (m, 4H), 6.63-6.57 (m,2H), 3.45 (s, 3H), 3.08-2.55 (m, 6H), 2.16 (s, 3H), 1.85-1.65 (m, 2H),1.55 (s, 18H), 1.45-1.16 (m, 2H), 1.16-1.08 (m, 2H), 0.91 (s, 3H), 0.85(t, 3H), 0.76 (s, 3H); rac-form isomer: δ 8.28 (dd, 1H), 7.84 (bs, 1H),7.46 (s, 1H), 7.37-7.23 (m, 3H), 7.19-7.08 (m, x H), 6.97 (s, 1H),6.94-6.83 (m, 4H), 6.68 (dd, 1H), 3.47 (s, 3H), 3.12-3.02 (m, 1H),2.98-2.72 (m, 4H), 2.50-2.40 (m, 1H), 1.95 (s, 3H), 1.84-1.72 (m, 2H),1.59 (s, 18H), 3.08-2.55 (m, 6H), 2.16 (s, 3H), 1.85-1.65 (m, 2H), 1.55(s, 18H), 1.38-1.10 (m, 4H), 0.94 (s, 3H), 0.87 (t, 3H), 0.69 (s, 3H).

MCN12 and MNC13

4-Phenyl-1H-indene

A 250 mL flask was charged with 4-bromo-1H-indene (10.00 g, 51.55 mmol),phenylboronic acid (6.60 g, 54.12 mmol), potassium carbonate (10.67 g,77.33 mmol), tetrabutylammonium bromide (3.42 g, 10.31 mmol),bis(triphenylphosphine) palladium(II) dichloride (1.80 g, 2.50 mmol),water (150 mL) and ethanol (15 mL). The reaction was refluxed for 3hours under N₂ atmosphere. The reaction was cooled down and extractedwith hexane (3×100 mL). The combined organic layers were dried overNa₂SO₄ and concentrated under reduced pressure. The resulting residuewas purified by flash chromatography over silica gel (eluent: hexane) toget the product (8.21 g) as colorless oil.

2-Bromo-7-phenyl-2,3-dihydro-1H-inden-1-ol

A pre-cooled (5° C.) solution of 4-phenyl-1H-indene (8.10 g, 42.2 mmol)in dimethyl sulfoxide (50 mL) and water (1 mL) was treated in oneportion with N-bromosuccinimide (8.26 g, 46.4 mmol), and the reactionwas allowed to warm up to room temperature naturally and stirred for 3hours. The mixture was poured into water (500 mL) and extracted withtoluene (3×50 mL). The combined organic phases were washed with water(100 mL) and dried over Na₂SO₄. The crude product in toluene was usedfor next step without further purification.

2-Bromo-4-phenyl-1H-indene

The solution from previous step was treated with p-toluenesulfonoc acidmonohydrate (0.4 g, 6.3 mmol) and the mixture was refluxed for 6 hourswhile removing water with a Dean-Stark trap. The mixture was cooled downand concentrated under reduced pressure. The residue was purified byflash chromatography over silica gel (eluent: hexane) to get2-bromo-4-phenyl-1H-indene (7.36 g) as white solid.

2-Butyl-4-phenyl-1H-indene

In glove box, n-butylmagnesium chloride (15.0 mL, 2.0 M in THF, 29.54mmol) was added to a solution of 2-bromo-4-phenyl-1H-indene (7.25 g,26.85 mmol) and PdCl₂(dppf)DCM (1.10 g, 1.34 mmol) in 30 mL of THF. Thereaction was heated up to 45° C. and stirred at this temperature for 3hours. The reaction was moved out the glove box and quenched with 200 mLof water. The mixture was extracted with hexane (50 mL×2). The combinedorganic phases were dried over Na₂SO₄ and concentrated under reducedpressure. The residue was purified by silica gel chromatography (eluent:hexane) to get product as colorless oil (2.93 g).

Lithium [1-(4-phenyl-2-butyl indenide)]

A precooled solution of 2-butyl-4-phenyl-1H-indene (2.71 g, 10.9 mmol)in diethyl ether (20 mL) was treated with nBuLi (2.5 M in hexane, 5.7mL, 11.4 mmol). The reaction was stirred at room temperature for 3 h.Then all volatiles were evaporated. The residue was washed with hexane(20 mL) and dried under vacuum to yield a green-yellow solid as theproduct (2.700 g).

Chlorodimethyl (4-phenyl-2-butyl-indenyl) silane

A precooled solution of lithium [1-(4-phenyl-2-butyl indenide)] (1.35 g,5.31 mmol) in diethyl ether (20 mL) was treated with Me2SiCl2 (3.43 g,26.57 mmol), and the resulting white slurry was stirred at roomtemperature overnight. After 19 hours stirring, all volatiles wereevaporated under reduced pressure. The residue was extracted with hexane(20 mL×2), and the combined filtrate was concentrated to dryness undervacuum to give colorless oil as product (1.79 g).

Dimethylsilyl (4-phenyl-2-butyl-indenyl) trifluoromethanesulfonate

A solution of chlorodimethyl (4-phenyl-2-butyl-indenyl) silane (1.78 g,5.26 mmol) in toluene (20 mL) was treated with silvertrifluoromethanesulfonate (1.48 g, 5.78 mmol) while stirring. The whiteslurry was stirred at room temperature for 3 h. Toluene was evaporatedunder vacuum and the residue was extracted with hexane (10 mL×2). Thefiltrate was concentrated in vacuo to give colorless oil as the product(2.17 g).

Bis(4-phenyl-2-butyl-indenyl) dimethylsilane

A precooled solution of dimethylsilyl (4-phenyl-2-butyl-indenyl)trifluoromethanesulfonate (2.10 g, 4.62 mmol) in diethyl ether (20 mL)was treated with lithium [1-(4-phenyl-2-butyl indenide)] (1.17 g, 4.62mmol). The solution was stirred for 5 hours at room temperature. Diethylether was evaporated. The residue was extracted with hexane (2×10 mL).The combined filtrate was concentrated and further dried in vacuo to getoff-white foam as the product (2.56 g).

Dilithium dimethylsilyl bis(4-phenyl-2-butyl indenide)

nBuLi (2.5 M in hexane, 3.7 mL, 9.28 mmol) was added to a precooledsolution of bis(4-phenyl-2-butyl-indenyl) dimethylsilane (2.50 g, 4.53mmol) in diethyl ether (20 mL). The solution was stirred at roomtemperature for 3 h. All volatiles were removed under vacuum. Theresidue was washed with hexane (10 mL×2) and dried in vacuo to give palepink solid as the desired dilithium salt (2.38 g).

Dimethylsilyl bis(4-phenyl-2-butyl-indenyl) zirconium dichloride

A precooled solution of dilithium dimethylsilyl bis(4-phenyl-2-butylindenide) (2.30 g, 4.08 mmol) in toluene (30 mL) was treated with ZrCl4(0.938 g, 4.08 mmol). The mixture was stirred at room temperature overweekend. After 64 hours stirring, the mixture was concentrated todryness. The residue was extracted with toluene (30 mL×2). The combinedfiltrate was concentrated under reduced pressure and washed with hexane(20 mL) to get an orange solid as a mixture of two isomers. The mixturewas recrystallized (20 mL of dichloromethene and 10 mL of diethyl ether,refluxed to room temperature, aged for 16 hours). The slurry wasfiltered and the pancake was washed with hexane (10 mL) to afford therac-isomer (yellow, 433 mg, ratio of rac/meso=6.7:1, MNC12). Thefiltrate was concentrated under reduced pressure and the residue waswashed with diethyl ether (30 mL) to obtain meso-isomer rich mixture(orange, 651 mg, ratio of rac/meso=1:1.8, MCN13). 1H NMR (400 MHz, C₆D6,23° C.), rac-form isomer: δ 7.88 (dd, 4H), 7.57 (d, 2H), 7.30 (dd, 2H),7.27 (s, 2H), 7.21 (t, 4H), 7.10-7.04 (m, 2H), 6.90 (dd, 2H), 2.76-2.66(m, 2H), 2.50-2.40 (m, 2H), 1.36-1.22 (m, 4H), 1.19-1.10 (m, 4H), 0.96(s, 6H), 0.75 (t, 6H); meso-form isomer (identified from rac/meso=1:1.8mixture): δ 7.83 (dd, 4H), 7.55 (d, 2H), 7.21 (dd, 6H), 7.13-6.99 (m,4H), 6.75 (dd, 2H), 2.85-2.70 (m, 4H), 1.40-1.05 (m, 8H), 1.10 (s, 3H),0.96 (s, 3H), 0.75 (t, 6H).

MCN 14

Dimethylsilyl (4-oPh.2.-2-hexyl indenyl)(4-(3′,5′-di-tert-butyl-4′-methoxyphenyl)-2-methyl indenyl) zirconiumdimethyl

A solution of rac-dimethylsilyl (4-oPh.2.-2-hexyl indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl indenyl) zirconiumdichloride (MCN1) (with 0.5 equiv. of toluene) (1.1 g) in diethyl ether(100 mL) was precooled at −35° C. for 15 min. MeMgBr (3.5 mL of 3Msolution in diethyl ether) was added and the reaction was stirred atroom temperature for 70 h. All volatiles were evaporated. The residuewas extracted with hexane (60 mL once, 20 mL three times). Filtrateswere combined and were evaporated to dryness. Hexane (15 mL) was addedand the slurry was left at −35° C. for 1 d to give 0.35 g ofdimethylsilyl (4-oPh.2.-2-hexyl indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl indenyl) zirconiumdimethyl, rac/meso: ˜44/1 (MCN14). ¹H NMR (400 MHz, C6D6, 23° C.),rac-isomer: δ 7.85 (m, 3H), 7.52 (d, 1H), 7.42-7.40 (m, 2H), 7.31 (d,1H), 7.25-7.22 (m, 3H), 7.12-7.18 (m, 3H), 6.99-6.88 (m, 4H), 6.77 (s,1H), 6.72 (dd, 1H), 3.41 (s, 3H), 2.65-2.59 (m, 1H), 2.17-2.09 (m, 1H),1.92 (s, 3H), 1.52 (s, 18H), 1.45-1.18 (m, 8H), 0.94 (t, 3H), 0.86 (s,3H), 0.66 (s, 3H), −0.54 (s, 3H), −0.61 (s, 3H).

Supported Methylalumoxane (SMAO)

SMAO was prepared as follows: Davison 948™ Silica (20.8606 g, calcinedat 130° C.) was slurried in 121 mL of toluene and chilled in the freezer(−35° C.). MAO (50.5542 g of a 30% wt solution in toluene) was addedslowly in 3 parts with the silica slurry returned to the freezer for afew minutes (approx. 2 min) between additions. The slurry was stirred atroom temperature for 2 hours, filtered with a fine glass frit filter,reslurried in 80 mL of toluene for 15 min at room temperature, and thenfiltered again. The solid was reslurried in 80 mL of toluene at 80° C.for 30 min and then filtered. The solid was reslurried in 80 mL oftoluene at 80° C. for 30 min and then filtered a final time. The celstirand solid were washed out with 40 mL of toluene. The solid was thenwashed with pentane and dried under vacuum for 24 hours. Collected28.9406 g of a free flowing white powder.

Preparation of Supported Catalysts

Supported Catalyst A: MCN1 (26.4 mg, 0.0288 mmol) and MAO (0.2409 g of a30% by weight toluene solution) were combined together in a 20 mL vialalong with 2 mL of toluene and stirred for 1 hr. SMAO (0.7200 g) wasslurried in 20 mL of toluene and chilled to −35° C. for a few minutes.The catalyst solution was added to the slurry. The slurry stirred for 1hr, occasionally being placed in the freezer to maintain a temperatureslightly below RT. The slurry was then stirred at 40° C. for 2 hr. Theslurry was filtered and the solid reslurried in 20 mL of toluene at 60°C. for 30 min before being filtered again. The solid was reslurriedtwice more at 60° C. The celstir was then washed out with 20 mL oftoluene which was also used to wash the solid. The solid was washedtwice with pentane and dried under vacuum to give 0.6000 g of pinksolid.

Supported Catalyst B: MCN2 (28.8 mg, 0.0313 mmol) and MAO (0.2620 g of a30% by weight toluene solution) were combined together in a 20 mL vialalong with 2 mL of toluene and stirred for 1 hr. SMAO (0.7885 g) wasslurried in 15 mL of toluene and chilled to −35° C. for a minute. Thecatalyst solution was added to the slurry. The slurry stirred for 1 hr,occasionally being placed in the freezer to maintain a temperatureslightly below RT. The slurry was then stirred at 40° C. for 2 hr. Theslurry was filtered and the solid reslurried in 15 mL of toluene at 60°C. for 30 min before being filtered again. The solid was reslurriedtwice more at 60° C. The celstir was then washed out with 15 mL oftoluene which was also used to wash the solid. The solid was washedtwice with pentane and dried under vacuum to give 0.7054 g of pinksolid.

Catalysts C, D, and F were prepared by analogous methodology.

Supported Catalyst E (Comparative): MCN10 (29.3 mg, 0.0402 mmol) and MAO(0.3316 g of a 30% by weight toluene solution) were combined together ina 20 mL vial along with 2 mL of toluene and stirred for 1 hr. SMAO(1.0079 g) was slurried in 15 mL of toluene and chilled to −35° C. for afew minutes. The catalyst solution was added to the slurry. The slurrystirred for 1 hr, occasionally being placed in the freezer to maintain atemperature slightly below RT. The slurry was then stirred at 40° C. for2 hr. The slurry was filtered and the solid reslurried in 15 mL oftoluene at 60° C. for 30 min before being filtered again. The solid wasreslurried twice more at 60° C. The celstir was then washed out with 15mL of toluene which was also used to wash the solid. The solid waswashed twice with pentane and dried under vacuum to give 0.9041 g ofpink solid.

General Procedure for Small Scale Polymerization

Unless stated otherwise propylene homopolymerization andethylene-propylene copolymerizations are carried out in a parallelpressure reactor, as generally described in U.S. Pat. Nos. 6,306,658;6,455,316; WO 00/09255; and Murphy et al., J. Am. Chem. Soc., 2003, 125,pp. 4306-4317, each of which is incorporated by reference herein in itsentirety. Although specific quantities, temperatures, solvents,reactants, reactants ratios, pressures, and other variables may need tobe adjusted from one reaction to the next, the following describes atypical polymerization performed in a parallel, pressure reactor.

For propylene polymerization and ethylene propylene copolymerizationwith unsupported metallocene catalysts, the following procedure wasused:

A pre-weighed glass vial insert and disposable stirring paddle werefitted to each reaction vessel of the reactor, which contains 48individual reaction vessels. The reactor was then closed and propylenegas was introduced to each vessel to purge the nitrogen out of thesystem. If any modules receive hydrogen, it was added in during thepurge process. The solvent (typically isohexane) was added nextaccording to the set total reaction volume, including the followingadditions, to 5 mL usually. At this time scavenger and/or co-catalystand/or a chain transfer agent, such as tri-n-octylaluminum in toluene(100-1000 nmol) was added. The contents of the vessels were stirred at800 rpm. The propylene was added as gas to a set pressure. The reactorvessels were heated to their set run temperature (usually between 50° C.and 110° C.). If any modules receive ethylene, it was added as a gas toa pre-determined pressure (typically 40-220 psi) above the pressure ofthe propylene while the reactor vessels were heated to a set runtemperature.

A toluene solution of catalyst (typically at a concentration of 0.2mmol/L in toluene which usually provides about 15 nmol of catalyst) wasinjected into the reactors. The reaction was then allowed to proceeduntil a pre-determined amount of pressure had been taken up by thereaction. Alternatively, the reaction may be allowed to proceed for aset amount of time. The reaction was quenched by pressurizing the vesselwith compressed air. After the polymerization reaction, the glass vialinsert containing the polymer product and solvent was removed from thepressure cell and the inert atmosphere glove box, and the volatilecomponents were removed using a Genevac HT-12 centrifuge and GenevacVC3000D vacuum evaporator operating at elevated temperature and reducedpressure. The vial was then weighed to determine the yield of thepolymer product. The resultant polymer was analyzed by Rapid GPC (seebelow) to determine the molecular weight and by DSC (see below) todetermine melting point.

For ethylene propylene copolymerization with supported metallocenecatalysts, the following procedure was used: A pre-weighed glass vialinsert and disposable stirring paddle were fitted to each reactionvessel of the reactor, which contained 48 individual reaction vessels.The reactor was then closed and propylene gas was introduced to eachvessel to purge the nitrogen out of the system. If any modules receivehydrogen, it was added during the purge process. The solvent (typicallyisohexane) was added next according to the set total reaction volume,including the following additions, to 5 mL usually. At this timescavenger and/or co-catalyst and/or a chain transfer agent, such astri-n-octylaluminum in toluene (100-1000 nmol) was added. The contentsof the vessels were stirred at 800 rpm. The propylene was added as gasto a set pressure. The reactor vessels were heated to their set runtemperature (usually between 50° C. and 110° C.). The ethylene was addedas a gas to a pre-determined pressure (typically 40-220 psi) above thepressure of the propylene while the reactor vessels were heated to a setrun temperature. The catalyst slurry was vortexed to suspend thecatalyst particles into a solution. The buffer toluene (typically 100microliters), the toluene solution of catalyst (typically 3 mg/mlconcentration), and another aliquot of toluene (500 microliters) wasthen injected into the reactors. The reaction was then allowed toproceed until a pre-determined amount of pressure had been taken up bythe reaction. Alternatively, the reaction may be allowed to proceed fora set amount of time. At this point, the reaction was quenched bypressurizing the vessel with compressed air. After the polymerizationreaction, the glass vial insert containing the polymer product andsolvent was removed from the pressure cell and the inert atmosphereglove box, and the volatile components were removed using a GenevacHT-12 centrifuge and Genevac VC3000D vacuum evaporator operating atelevated temperature and reduced pressure. The vial was then weighed todetermine the yield of the polymer product. The resultant polymer wasanalyzed by Rapid GPC (see below) to determine the molecular weight andby DSC (see below) to determine melting point. Data are reported inTable 1 to 4.

To determine various molecular weight related values by GPC, hightemperature size exclusion chromatography was performed using anautomated “Rapid GPC” system as generally described in U.S. Pat. Nos.6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632;6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is fullyincorporated herein by reference for US purposes. This apparatus has aseries of three 30 cm×7.5 mm linear columns, each containing PLgel 10um, Mix B. The GPC system was calibrated using polystyrene standardsranging from 580-3,390,000 g/mol. The system was operated at an eluentflow rate of 2.0 mL/minutes and an oven temperature of 165° C.1,2,4-trichlorobenzene was used as the eluent. The polymer samples weredissolved in 1,2,4-trichlorobenzene at a concentration of 0.1-0.9 mg/mL.250 uL of a polymer solution was injected into the system. Theconcentration of the polymer in the eluent was monitored using a PolymerChar IR4 detector. The molecular weights presented are relative tolinear polystyrene standards and are uncorrected. For purposes of thisinvention only, the Rapid-GPC Mw (weight average molecular weight) datacan be divided by 1.9 to approximate GPC-3D Mw results forethylene-propylene copolymers. Likewise, purposes of this inventiononly, the Rapid-GPC Mw data for propylene homopolymers can be divided by1.5 to approximate GPC-3D Mw results.

Differential Scanning Calorimetry (DSC Procedure-1) measurements wereperformed on a TA-Q200 instrument to determine the melting point of thepolymers. Samples were pre-annealed at 220° C. for 15 minutes and thenallowed to cool to room temperature overnight. The samples were thenheated to 220° C. at a rate of 100° C./minutes and then cooled at a rateof 50° C./min. Melting points were collected during the heating period.

The amount of ethylene incorporated in the polymers (weight %) wasdetermined by rapid FT-IR spectroscopy on a Bruker Vertex 70 IR inreflection mode. Samples were prepared in a thin film format byevaporative deposition techniques. Weight percent ethylene was obtainedfrom the ratio of peak heights at 729.8 and 1157.9 cm-1. This method wascalibrated using a set of ethylene/propylene copolymers with a range ofknown wt % ethylene content.

General Procedure for Solution Polymerization in Coninuous Stirred TankReactor (Table 5, Examples 162-167)

Polymerizations were carried out in a continuous stirred tank reactorsystem. A 1-liter Autoclave reactor was equipped with a stirrer, apressure controller, and a water cooling/steam heating element with atemperature controller. The reactor was operated in liquid fillcondition at a reactor pressure in excess of the bubbling point pressureof the reactant mixture, keeping the reactants in liquid phase. Allfeeds (solvent and monomers) were pumped into the reactors using Pulsafeed pumps and the flow rates were controlled using Coriolis mass flowcontroller (Quantim series from Brooks) except for the ethylene, whichflowed as a gas under its own pressure through a Brooks flow controller.Ethylene and propylene feeds were combined into one stream and thenmixed with a pre-chilled isohexane stream that had been cooled to atleast 0° C. The mixture was then fed to the reactor through a singleline. Scavenger solution was added to the combined solvent and monomerstream just before it entered the reactor to further reduce any catalystpoisons. Similarly, catalyst solution was fed to the reactor using anISCO syringe pump through a separated line. Isohexane (used as solvent),and monomers (e.g., ethylene and propylene) were purified over beds ofalumina and molecular sieves. Toluene for preparing catalyst solutionswas purified using the same technique. An isohexane solution oftri-n-octyl aluminum (TNOA) (25 wt % in hexane, Sigma Aldrich) was usedas scavenger solution. The catalyst MTC14 was activated withN,N-dimethyl anilinium tetrakis (pentafluorophenyl) borate at a molarratio of about 1:1 in 900 ml of toluene.

The polymer produced in the reactor exited through a back pressurecontrol valve that reduced the pressure to atmospheric. This caused theunconverted monomers in the solution to flash into a vapor phase whichwas vented from the top of a vapor liquid separator. The liquid phase,comprising mainly polymer and solvent, was collected for polymerrecovery. The collected samples were first air-dried in a hood toevaporate most of the solvent, and then dried in a vacuum oven at atemperature of about 90° C. for about 12 hours. The vacuum oven driedsamples were weighed to obtain yields. Conversion was calculated basingon the yield and feed rate of all monomers.

The detailed polymerization process conditions and some characteristicproperties are listed in Table 5. The scavenger feed rate was adjustedto optimize the catalyst efficiency and the feed rate varied from 0 (noscavenger) to 15 tmol/min. The catalyst feed rates may also be adjustedaccording to the level of impurities in the system to reach the targetedconversions listed. Isohexane was used as the solvent for polymerizationand its feed rate was 56.7 gram/min. All the reactions were carried outat a pressure of about 2.4 MPa/g unless otherwise mentioned. Additionalprocessing conditions for the polymerization process of Example 162-167,and the properties of the polymers produced are included below in Table5.

Ethylene content is determined using FTIR according the ASTM D3900.

Melt flow rate (MFR) was determined according to ASTM D1238 using a loadof 2.16 kg and at a temperature of 230° C. High Load Melt Index (alsoreferred to as 121) is the melt flow rate measured according to ASTMD-1238 at 190° C., under a load of 21.6 kg. The units for HLMI are g/10min or dg/min. Melt Index Ratio (MIR) is the ratio of the high load meltindex to the melt index, or I21/I2.

The number of vinyl chain ends, vinylidene chain ends and vinylene chainends is determined using ¹H NMR using 1,1,2,2-tetrachloroethane-d2 asthe solvent on an at least 400 MHz NMR spectrometer. Proton NMR data iscollected at 120° C. in a 5 mm probe using a Varian spectrometer with a1H frequency of 400 MHz. Data is recorded using a maximum pulse width of45°, 5 seconds between pulses and signal averaging 120 transients.Spectral signals are integrated and the number of unsaturation types per1000 carbons are calculated by multiplying the different groups by 1000and dividing the result by the total number of carbons.

The chain end unsaturations are measured as follows. The vinylresonances of interest are between from 5.0 to 5.1 ppm (VRA), thevinylidene resonances between from 4.65 to 4.85 ppm (VDRA), the vinyleneresonances from 5.31 to 5.55 ppm (VYRA), the trisubstituted unsaturatedspecies from 5.11 to 5.30 ppm (TSRA) and the aliphatic region ofinterest between from 0 to 2.1 ppm (IA).

The number of vinyl groups/1000 Carbons is determined from the formula:(VRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA). Likewise, the number ofvinylidene groups/1000 Carbons is determined from the formula:(VDRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA), the number of vinylenegroups/1000 Carbons from the formula (VYRA*500)/((IA+VRA+VYRA+VDRA)/2)25+TSRA) and the number of trisubstituted groups from the formula(TSRA*1000)/((IA+VRA+VYRA+VDRA)/2)+TSRA). VRA, VDRA, VYRA, TSRA and IAare the integrated normalized signal intensities in the chemical shiftregions defined above. Vinyl chain ends are reported as a molarpercentage of the total number of moles of unsaturated polymerend-groups (that is, the sum of vinyl chain ends, vinylidene chain ends,vinylene chain ends, and trisubstituted olefinic chain ends).

Small Amplitude Oscillatory Shear (SAOS): Dynamic shear melt rheologicaldata was measured with an Advanced Rheometrics Expansion System (ARES)using parallel plates (diameter=25 mm) in a dynamic mode under nitrogenatmosphere. For all experiments, the rheometer was thermally stable at190° C. for at least 30 minutes before inserting compression-moldedsample of resin (polymer composition) onto the parallel plates. Todetermine the samples' viscoleastic behavior, frequency sweeps in therange from 0.01 to 385 rad/s were carried out at a temperature of 190°C. under constant strain of 10%. A nitrogen stream was circulatedthrough the sample oven to minimize chain extension or cross-linkingduring the experiments. A sinusoidal shear strain is applied to thematerial. If the strain amplitude is sufficiently small the materialbehaves linearly. As those of ordinary skill in the art will be aware,the resulting steady-state stress will also oscillate sinusoidally atthe same frequency but will be shifted by a phase angle δ with respectto the strain wave. The stress leads the strain by δ. For purely elasticmaterials δ=0° (stress is in phase with strain) and for purely viscousmaterials, δ=90° (stress leads the strain by 90° although the stress isin phase with the strain rate). For viscoleastic materials, 0<δ<90.Complex shear viscosity, loss modulus (G″) and storage modulus (G′) asfunction of frequency are provided by the small amplitude oscillatoryshear test. Dynamic viscosity is also referred to as complex viscosityor dynamic shear viscosity. The phase or the loss angle δ, is theinverse tangent of the ratio of G″ (shear loss modulus) to G′ (shearstorage modulus).

Differential Scanning Calorimetry (for larger scale products)(DSC-Procedure-2). Peak melting point, (Tm, also referred to as meltingpoint), peak crystallization temperature (Tc, also referred to ascrystallization temperature), glass transition temperature (Tg), heat offusion (Hf), and percent crystallinity were determined using thefollowing DSC procedure according to ASTM D3418-03. Differentialscanning calorimetric (DSC) data were obtained using a TA Instrumentsmodel Q2100 machine. Samples weighing approximately 5-10 mg were sealedin an aluminum hermetic sample pan. The DSC data were recorded by firstgradually heating the sample to 200° C. at a rate of 10° C./minute. Thesample was kept at 200° C. for 2 minutes, then cooled to −70° C. at arate of 10° C./minute, followed by an isothermal for 2 minutes andheating to 200° C. at 10° C./minute. Both the first and second cyclethermal events were recorded. Areas under the endothermic peaks weremeasured and used to determine the heat of fusion and the percent ofcrystallinity. The percent crystallinity is calculated using theformula, [area under the melting peak (Joules/gram)/B(Joules/gram)]*100, where B is the heat of fusion for the 100%crystalline homopolymer of the major monomer component. These values forB are to be obtained from the Polymer Handbook, Fourth Edition,published by John Wiley and Sons, New York 1999, provided, however, thata value of 189 J/g is used as the heat of fusion for 100% crystallinepolypropylene, a value of 290 J/g is used for the heat of fusion for100% crystalline polyethylene. The melting and crystallizationtemperatures reported here were obtained during the first cooling/secondheating cycle unless otherwise noted.

In the event of conflict between the DSC Procedure-1 and DSCprocedure-2, DSC procedure-2 shall be used.

Gel Permeation Chromotography with Three Detectors (GPC-3D)

Mw, Mn and Mw/Mn are determined by using a High Temperature GelPermeation Chromatography (Agilent PL-220), equipped with three in-linedetectors, a differential refractive index detector (DRI), a lightscattering (LS) detector, and a viscometer.

Experimental details, including detector calibration, are described in:T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules,Volume 34, Number 19, pp. 6812-6820, (2001) and references therein.Three Agilent PLgel 10 μm Mixed-B LS columns are used. The nominal flowrate is 0.5 mL/min, and the nominal injection volume is 300 μL. Thevarious transfer lines, columns, viscometer and differentialrefractometer (the DRI detector) are contained in an oven maintained at145° C. Solvent for the experiment is prepared by dissolving 6 grams ofbutylated hydroxytoluene as an antioxidant in 4 liters of Aldrichreagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is thenfiltered through a 0.1 μm Teflon filter. The TCB is then degassed withan online degasser before entering the GPC-3D. Polymer solutions areprepared by placing dry polymer in a glass container, adding the desiredamount of TCB, then heating the mixture at 160° C. with continuousshaking for about 2 hours. All quantities are measured gravimetrically.The TCB densities used to express the polymer concentration inmass/volume units are 1.463 g/ml at room temperature and 1.284 g/ml at145° C. The injection concentration is from 0.5 to 2.0 mg/ml, with lowerconcentrations being used for higher molecular weight samples. Prior torunning each sample the DRI detector and the viscometer are purged. Flowrate in the apparatus is then increased to 0.5 ml/minute, and the DRI isallowed to stabilize for 8 hours before injecting the first sample. TheLS laser is turned on at least 1 to 1.5 hours before running thesamples. The concentration, c, at each point in the chromatogram iscalculated from the baseline-subtracted DRI signal, IDRI, using thefollowing equation:c=K _(DRI) I _(DR)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and λ=690 nm. Units on parametersthroughout this description of the GPC-3D method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature DAWN HELEOS. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient. P(θ) is the formfactor for a monodisperse random coil, and K_(o) is the optical constantfor the system:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{dn}/{dc}} \right)}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system, which take the same value as the one obtainedfrom DRI method. The refractive index, n=1.500 for TCB at 145° C. andX=657 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:η_(s) =c[Θ]+0.3(c[Θ])²

where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theGPC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

M_(v) is the viscosity-average molecular weight based on molecularweights determined by LS analysis. Z average branching index (g′_(Zave))is calculated using Ci=polymer concentration in the slice i in thepolymer peak times the mass of the slice squared, Mi²

The Mark-Houwink parameters used in the data processing for the testedsamples are: 1) for ethylene polymers: K/a=0.000579/0.695; and 2) forpropylene polymers: K/a=0.0002288/0.705).

All molecular weights are weight average unless otherwise noted. Allmolecular weights are reported in g/mol unless otherwise noted.

In the event of conflict between the GPC-3D procedure and the “RapidGPC,” the GPC-3D procedure immediately above shall be used. Furtherdetails regarding methods of determining Mw, Mn, MWD are described in US2006/0173123 pages 24-25, paragraphs [0334] to [0341].

1% Secant flexural modulus is measured using an ISO 37-Type 3 bar, witha crosshead speed of 1.0 mm/min and a support span of 30.0 mm using anInstron machine according to ASTM D 790 (A, 1.0 mm/min).

TABLE 1 Small Scale Ethylene Propylene Copolymerization with unsupportedMetallocene Catalysts. Catalyst = 0.015 μmol, MAO = 500 equiv.,isohexane solvent, 115 psi propylene, total volume = 5 mL, T_(p) = 70°C. Average Activity (kg Average Activity (kg C2 C2 Mw Mw/ Rxn YieldPolymer/ Mw Polymer/ Ex. Catalyst (psi) wt % (g/mol) Mn Time(s) (g) mmolcat.h) (kg/mol) mmol cat.h) 1 MCN1 80 21.6 459420 1.8 51 0.175 825 559615 2 120 28.9 423657 2.0 60 0.2748 1096 416 1277 3 160 48.7 376825 2.261 0.3387 1339 399 1555 4 80 18.9 561347 1.7 69 0.177 618 5 120 30.5408237 1.8 64 0.2877 1081 6 160 36.3 388266 2.2 62 0.3522 1357 7 80 21657550 1.8 96 0.1598 402 8 120 29 417125 2.9 53 0.3643 1656 9 160 39432858 2.8 45 0.3661 1970 10 MCN5 80 24 351890 1.9 64 0.2067 778 347 84911 120 33 259567 2.6 27 0.3586 3176 267 3052 12 160 41 251166 3.2 290.3641 3066 272 2744 13 80 25 342108 2.0 61 0.2332 921 14 120 33 2753792.2 28 0.3367 2928 15 160 40 293719 2.4 35 0.3573 2422 16 MCN6 80 26.2289457 1.8 48 0.2241 1128 284 1188 17 120 30.4 259386 1.8 48 0.2815 1416252 1385 18 160 41.2 241206 2.0 43 0.2847 1596 238 1802 19 80 22.0278571 1.8 51 0.2637 1248 20 120 31.8 245195 1.9 48 0.2702 1354 21 16038.5 234337 1.9 35 0.2885 2007 22 MCN7 80 21.9 267204 1.7 90 0.1605 429267 424 23 120 30.6 295011 1.9 77 0.1747 546 295 546 (one (one datum)datum) 24 160 38.4 284000 2.3 69 0.2704 941 280 963 25 80 20.8 2670411.7 87 0.1516 419 26 160 34.0 276333 2.0 70 0.2864 985

TABLE 2 Small Scale Propylene Polymerization and Ethylene PropyleneCopolymerization Using 0.39 mg of Supported Catalysts. Conditions:isohexane solvent, 115 psi propylene, TONAL = 4 μmol, total volume = 5mL, T_(p) = 70° C. Activity C2 Run Yield (gPolymer/ Mw Mw/ C2 Tm Ex.Catalyst (psi) Time(s) (mg) gcat-sup.hr) (kg/mol) Mn wt % (° C.) 27 A2700 32.7 112 1006 2.5 0.0 151.5 28 40 2700 66.3 227 595 2.0 10.5 29 1201649 87.2 488 535 1.8 29.4 30 160 318 87.7 2546 500 1.7 36.4 31 220 15397.4 5876 479 1.7 48 32 2701 31.1 106 1012 2.6 0.0 151.7 33 40 2701 66.3227 574 1.8 12.8 34 120 815 90.7 1027 510 1.9 27.9 35 160 442 80.9 1690486 2.2 34.4 36 220 196 86.7 4083 540 1.8 42.3 37 B 2701 40.0 137 12332.3 0.0 150.8 38 40 2701 60.4 206 779 2.0 10.1 39 120 2079 80.0 355 7251.9 24.2 40 160 797 81.7 946 676 1.8 34.6 41 220 237 82.2 3202 655 1.843 42 2700 40.6 139 1055 2.3 0.0 151.2 43 40 2700 64.3 220 818 1.9 9.744 120 1281 88.7 639 737 1.9 23.9 45 160 723 84.5 1079 658 2.1 29.2 46220 260 81.2 2883 604 2.1 44.3 47 C 2701 49.3 168 1112 2.6 0.0 151 48 402701 75.1 257 816 1.9 10.1 49 120 242 99.4 3791 606 2.4 23.2 50 160 194112.1 5334 608 2.2 27.2 51 220 143 124.7 8049 534 2.3 39.4 52 2700 38.0130 1174 3.0 0.0 150.8 53 40 2700 59.0 202 677 2.4 10.4 54 120 257 100.83620 590 2.4 23.2 55 160 186 110.5 5484 554 2.0 26.1 56 220 142 117.07606 526 1.9 36.6 57 D 2701 37.1 127 449 2.9 0.0 153.3 58 40 533 126.12184 86 2.0 12 59 80 280 126.5 4170 77 2.4 19.3 60 120 287 139.3 4480 822.2 28.3 61 160 165 152.9 8554 99 2.6 34.4 62 220 110 192.2 16129 1362.0 46.8 63 2700 36 123 433 2.5 0.0 152.6 64 40 509 125.8 2281 90 2.814.4 65 80 306 143.6 4332 81 1.9 20.3 66 120 238 150.9 5853 85 2.1 26.667 160 188 194.2 9535 99 2.3 30.9 68 220 108 185.5 15855 131 2.0 42 69 E2700 25.3 86 294 2.3 0.0 148.8 70 40 2472 112.6 420 226 1.8 10.3 71 120508 98.4 1788 397 1.9 24.8 72 160 370 92.6 2310 453 1.7 34.5 73 220 22492.8 3824 584 1.8 46.2 74 2701 25.2 86 293 2.5 0.0 149.8 75 40 2700 88.1301 238 1.9 11.5 76 120 2527 90.1 329 413 1.8 27.8 77 160 608 89.9 1365483 1.9 32.4 78 220 287 91.9 2956 569 2.0 38 79 F 2700 18.8 64 1073 3.40 153.9 80 40 2701 73.8 252 364 2.4 13.7 81 80 2700 85.8 293 306 2.520.5 82 120 345 98.3 2630 272 2.5 25.9 83 160 176 95 4983 315 2.1 34.784 220 2701 64.1 219 347 2.1 46.8 85 2700 15.4 53 1078 3 0 153.7 86 402701 32.8 112 339 2.4 13.7 87 80 2700 33.2 114 318 2.3 24.4 88 120 22198.8 4127 280 2.9 25.5 89 160 1673 76.3 421 339 2.3 35.7 90 220 131 90.76391 355 2.3 37.5

TABLE 3 Small Scale Propylene Polymerization and Ethylene PropyleneCopolymerization with Unsupported Metallocene Catalysts: Catalyst =0.015 μmol, MAO = 500 equiv., isohexane solvent, 115 psi propylene,total volume = 5 mL, T_(p) = 70° C. run Activity (kg C2 feed Tm C2 Mw MnMw/ time Polymer/mmol Ex. Catalyst (psi) (° C.) wt % (g/mol) (g/Mol) Mn(s) yield (g) cat.h) 91 MCN 11 0 157.1 0.0 184861 110586 1.7 265 0.041538 (Comparative) 92 40 14.6 279427 152312 1.8 74 0.1035 338 93 80 22.0325857 149374 2.2 67 0.1622 580 94 120 32.8 354517 164011 2.2 57 0.1948819 95 160 41.2 395939 152487 2.6 54 0.295 1321 96 220 46.7 457238123981 3.7 43 0.3524 1953 97 0 157.3 0.0 209743 110975 1.9 315 0.0536 4198 40 13.9 285770 159029 1.8 104 0.13 300 99 80 19.9 337130 173287 1.980 0.1699 513 100 120 31.6 337589 142080 2.4 62 0.2007 773 101 160 36.8369463 137742 2.7 55 0.2717 1188 102 220 47.6 419041 112517 3.7 480.3633 1813 103 MCN4 0 156.5 0.0 625197 243080 2.6 109 0.2104 463 104 4013.3 512041 144269 3.5 75 0.3493 1119 105 80 17.9 517318 144917 3.6 530.3592 1624 106 120 22.9 611592 200172 3.1 58 0.34 1412 107 160 30.7545897 173431 3.1 43 0.3617 2023 108 220 48.0 531302 154863 3.4 260.4121 3761 109 0 158.2 0.0 697661 336538 2.1 90 0.1717 457 110 40 12.5537170 163253 3.3 73 0.3195 1055 111 80 18.3 454159 112961 4.0 61 0.37221476 112 120 25.1 482617 111828 4.3 36 0.3379 2278 113 160 31.9 597393241896 2.5 50 0.3572 1721 114 220 45.5 468942 78908 5.9 24 0.4351 4297

TABLE 4 Small Scale Propylene Polymerization and Ethylene PropyleneCopolymerization with Unsupported Metallocene Catalysts. Catalyst =0.015 μmol, MAO = 500 equiv., isohexane solvent, total volume = 5 mL.T_(p) = 70° C., 115 psi propylene T_(p) = 100° C., 160 psi propylene.Average C2 run Activity (kg Average (kg Average T_(p) feed time yieldPolymer/ Mw Mn Mw/ Tm C2 Polymer/ Mw Average Ex. Catalyst (° C.) (psi)(s) (g) mmol cat.h) (g/mol) (g/mol) Mn (° C.) wt % mmol cat.h) (kg/mol)Tm (° C.) 115 MCN1 70 123 0.1468 286 638251 320351 1.99 158.1 321 616157.2 116 MCN1 70 40 50 0.1448 691 530555 262300 2.02 12.6 759 492 117MCN1 70 80 41 0.1222 708 592607 324278 1.83 15.9 991 498 118 MCN1 70 12040 0.3687 2196 349989 128391 2.73 26.8 1957 353 119 MCN1 70 160 32 0.3992965 350848 96373 3.64 30.9 2728 394 120 MCN1 100 100 0.0835 201 203677104256 1.95 154.0 217 199 154.0 121 MCN1 70 125 0.1866 357 592988 2533922.34 156.3 122 MCN1 70 40 74 0.2536 828 453878 164790 2.75 11.4 123 MCN170 80 57 0.3011 1274 403790 165781 2.44 16.4 124 MCN1 70 120 47 0.33811719 356927 139351 2.56 25.0 125 MCN1 70 160 32 0.3269 2491 438004159199 2.75 31.2 126 MCN1 100 105 0.1016 233 194069 90182 2.15 154.0 127MCN3 70 97 0.1411 351 342613 161455 2.12 157.4 326 336 157.5 128 MCN3 7040 63 0.2216 848 319020 142080 2.25 9.4 729 329 129 MCN3 70 80 68 0.2616926 327786 152535 2.15 16.6 926 (1 data) 328 (1 data) 130 MCN3 70 120 470.3152 1616 311449 129634 2.40 24.1 1530 298 131 MCN3 70 160 37 0.30081951 299965 101396 2.96 30.3 1706 292 132 MCN3 100 86 0.1023 285 9449949523 1.91 154.4 277 95 154.5 133 MCN3 70 106 0.1334 301 330271 1539232.15 157.6 134 MCN3 70 40 72 0.1819 609 338657 161551 2.10 10.7 135 MCN370 120 55 0.3313 1443 283640 93431 3.04 23.4 136 MCN3 70 160 42 0.25671460 283476 70895 4.00 29.3 137 MCN3 100 99 0.1107 269 95569 46739 2.04154.6 138 MCN12 70 163 0.0972 143 319652 175225 1.82 156.6 147 321 156.7(Comparative) 139 MCN12 70 40 101 0.1256 298 243944 145030 1.68 10.7 307236 (Comparative) 140 MCN12 70 80 65 0.1449 535 219419 117694 1.86 18.4511 223 (Comparative) 141 MCN12 70 120 55 0.2117 927 217947 134045 1.6325.6 936 216 (Comparative) 142 MCN12 70 160 41 0.2161 1256 235345 1223321.92 37.6 1243 235 (Comparative) 143 MCN12 100 151 0.0776 123 7777941803 1.86 149.8 117 75 149.9 (Comparative) 144 MCN12 70 154 0.096 150321603 180173 1.78 156.8 (Comparative) 145 MCN12 70 40 96 0.1254 315227950 124343 1.83 9.3 (Comparative) 146 MCN12 70 80 76 0.1542 488227108 132918 1.71 16.9 (Comparative) 147 MCN12 70 120 55 0.2178 945214841 120123 1.79 27.3 (Comparative) 148 MCN12 70 160 43 0.222 1230233690 124533 1.88 35.7 (Comparative) 149 MCN12 100 165 0.076 111 7166842195 1.70 150.0 (Comparative) 150 MCN13 70 318 0.0536 40 333392 1793861.86 152.5 42 326 152.5 (Comparative) 151 MCN13 70 40 146 0.0602 99244292 98731 2.47 12.1 96 250 (Comparative) 152 MCN13 70 80 109 0.0725159 226541 97037 2.33 23.0 154 226 (Comparative) 153 MCN13 70 120 870.0951 263 214864 95954 2.24 29.4 243 210 (Comparative) 154 MCN13 70 16075 0.1069 343 231798 112833 2.05 41.4 327 236 (Comparative) 155 MCN13100 272 0.0477 42 73399 34040 2.16 147.7 48 72 147.7 (Comparative) 156MCN13 70 246 0.0457 45 318266 169933 1.87 152.5 (Comparative) 157 MCN1370 40 134 0.0515 93 254881 124105 2.05 11.8 (Comparative) 158 MCN13 7080 104 0.0646 149 226121 102127 2.21 21.0 (Comparative) 159 MCN13 70 12087 0.0811 223 205506 80948 2.54 29.7 (Comparative) 160 MCN13 70 160 760.0988 310 240107 120258 2.00 42.2 (Comparative) 161 MCN13 100 1590.0362 55 71599 38520 1.86 147.8 (Comparative)

TABLE 5 Continuous Propylene-Ethylene Solution Copolymerization withMCN14/N,N- dimethylanilinium tetrakis(perfluorophenyl)borate, in 1 Lreactor: TNOAL 25 wt %, 7.43E−06, mol/min; isohexane, 56.7 g/min Ex. 162163 164 165 166 167 Polymerization temp. (° C.) 70 120 120 70 70 70Ethylene feed rate (g/min) 0.57 6.79 6.79 3.39 2.26 1.70 Propylene feedrate (g/min) 14.0 6.0 1.0 14.0 14.0 14.0 MTC14 feed rate (mol/min)2.662E−07 2.282E−07 1.521E−07 6.085E−08 6.085E−08 6.085E−08 Polymer made(gram) 185 111.8 71 605.6 413.6 398.5 Conversion (%) 31.8% 41.6% 29.4%87.0% 84.8% 84.6% Complex shear viscosity at 0.1 rad/sec 81,0211,140,890 and 190° C. (Pa · s) Complex shear viscosity at 100 rad/sec2,107 6,703 and 190° C. (Pa · s) Phase angle at complex 48.7 modulus G*= 10,000 Pa (degree) Phase angle at complex 41.0 19.3 modulus G* =100,000 Pa (degree) MFR (g/10 min) 5.50 0.27 33.89 43.74 42.41 I21 (g/10min) 0.36 Mn_DRI (g/mol) 175,749 50,650 80,583 Mw_DRI (g/mol) 362,988138,672 253,017 Mz_DRI (g/mol) 590,173 256,227 505,327 Mw/Mn 2.07 2.742.81 g′_(vis) 1.036 0.935 0.886 Tc (° C.) 85.8 77.7 8.5 37.8 Tm (° C.)128.5 92.6 57.1 78.6 Tg (° C.) −41.6 −34.5 −34.9 Heat of fusion (J/g)79.8 102.7 25.8 40.2 Ethylene content (wt %) 3.42 64.07 90.28 21.0516.22 14.28 Vinyl chain ends/1000 Carbon 0.11 0.13 0.04 Vinyl chain end(%) 21.6% 31.0% 40.0%

As shown in Table 1 and FIG. 2, MTC1 with 2-hexyl substitution has shownhigher Mw capabilities than MTC5 (comparative) and MTC6 (comparative)with 2-Cyclopropyl substitution as well as MTC7 (comparative) with 2-iPrsubstitution in propylene-ethylene copolymerization under similarconditions.

As shown in Table 2 and FIG. 3, supported catalysts A, B, C with2-linear alkyl (at least 4 carbons) substitution have shown high Mwcapabilities for propylene polymers and copolymers fromhomo-polypropylene to low C2 (˜10 wt % C2) to high C2 (about 50 C2 wt%). As a comparison, comparative Catalyst D with 2-cyclopropylsubstitution has medium Mw capabilities for homo-polypropylene but verylow Mw capabilities for propylene-ethylene copolymers, comparativeCatalyst E with 2-iPr substitution has low Mw capabilities forhomo-polypropylene and low C2 (˜10 wt % C2) copolymers and high Mwcapabilities for high C2 (about 50 C2 wt %) copolymers, comparativeCatalyst F with 2-Me substitution has high Mw capabilities forhomo-polypropylene but only medium Mw capabilities forpropylene-ethylene copolymers.

As shown in Table 3 and FIG. 4, MTC4 with 2-Butyl substitution has shownhigher Mw capabilities than MTC 11 (comparative) with 2-iPr substitutionfor homo-polypropylene and propylene-ethylene copolymers.

As shown in Table 4 and FIGS. 5 and 6, MTC 1 and MTC3 with 4-substitutedphenyl groups have shown higher iPP Tm and Mw capabilities thancomparative metallocenes MTC12 and MTC13 for propylene polymerizationunder similar conditions.

As shown in Table 4 and FIGS. 7 and 8, MTC 1 and MTC3 with 4-substitutedphenyl groups have shown higher Mw capabilities and activities thancomparative metallocenes MTC12 and MTC13 for propylene-ethylenecopolymerization under similar conditions.

Interestingly, as shown in Table 5 and FIG. 9, inventive catalyst MTC14has shown not only good thermal stability and productivities at hightemperature (120° C.) but also produced polymers with long-chainbranching as evidenced by g′_(vis) of 0.935 (Ex. 163) and 0.886 (Ex.164). Rheological measurements as shown in FIGS. 10-12 further supportthis.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including.” Likewise whenever a composition,an element or a group of elements is preceded with the transitionalphrase “comprising,” it is understood that we also contemplate the samecomposition or group of elements with transitional phrases “consistingessentially of,” “consisting of,” “selected from the group of consistingof,” or “is” preceding the recitation of the composition, element, orelements and vice versa.

The invention claimed is:
 1. A metallocene catalyst compound representedby one or more of the following formulas:


2. The metallocene catalyst compound of claim 1, wherein the rac/mesoratio is 10:1 or greater.
 3. A catalyst system comprising activator andthe metallocene compound of claim 1, and optional support.
 4. Thecatalyst system of claim 3, wherein the activator comprises alumoxane,non-coordinating anion activator, or alumoxane and a non-coordinatinganion activator.
 5. A process to polymerize olefins comprisingcontacting one or more olefins with the catalyst system of claim 3.